- Email: [email protected]
Organic reactions of selected π-complexes annual survey covering the year 1981
ORGANIC RdACTIOW
OF SgLYCT.&:D ~-~OIq~PL~~S
AMXUAL SURViY COVdRI::G THS YZAR 1981’” GEORG& NARR and BERNARD d.
ROCKETT
Department of Physical Sciences, The Polytechnic, ~~olverhampton
XVI 1LY (Great Britain)
1.
Reviews
2.
General Results
3.
b-p$&pwo)4
4.
kj-CgH6&W+
(i) Formation (ii) Spectroscopic and Physico-chemical
5.
StUdi8s
(iii) General. Chemistry
16
(r\-CsRbf+
24
6.
[(y-C7H7)C~(CO)3]+
7.
(~-CgR~Dfn(C0)3
29
(i) Formation
29
and (C7Ra)Cr(CO)3
(ii) Spectroscopic and Physico-chemical Studies (iii) General Chemistry (iv) Applications
27
30 33 46
8.
Polynuclear (~-C~H~)~~(~O)~ Complexes
47
9.
Carbene and Carbyne (~-C5R~)I?n(CO)3 Complexes
50
IO.
(~-Trimethylenemethane)Fe(CO)~ Complexes
53
11.
(Acyclic-y-diene)Fe(C0)3 Complexes
54
12.
(~-c~H~)F~(C~)~
65
Organic Reactions of SelectedTT-Complexes, Annual. Survey Covering the Year 1980 see J. Organometal. Chem., 230 j1982) 261-374. References p. 128
2 I?.
68
(Cyclic-~-diene)Fe(CO)~ Complexes ii)
68
Formation
78
(ii) Spectroscopic and Physico-chzrnical Studies (iii) iGenera Cnemistry
82
1f.1 .
[(r,-c';j!5)ii'B(?-CgI::,)]f
95
15.
(n,-CsI!s)23u
16 .
(?-!:lc"iiiCo(n-CSEIS)
17.
(y-C53S)2Cn
18.
Cobalt-carbon Cluster Compounds
118
19.
(-~,,-C~iS~)~l$i.
123
20.
(7\-C8Lti)*U
126
and (q-CgES)20s
and
105 107
[(q,-~C$15)2Co]+
111
References
1.
128
Reviews
Jonas has reviewed the chemistry of a1:ali metal-transition metal T-complexes.
Dhis review contained a section on the preparation
of trrnsition metal-olefin 2nd alkali metal-transition metal-olefin complexes from metallocenes, mainly cobaltocene and ferrocene, by reductive elimination of the cgclopentadienyl ligand [I]. F'roboese has revieued the antitumor activity of metallocenes :iatts has reviewed tire chemistry of -cgclopentadienyl, 14‘ r\-arene a;!drelated complexes :,ublished in'lL>*/S(33. Ueeming has presented a brief review of the ruce:itly 7,ublished chemistry ofT-'oonded organometallics Clc3. Eowell has revietjed the chemistry of hydrocarbon-metal 8complexes published in 1979 (51.
The role ofG-T
rearranpme3t
of organotransition metal complexes has been reviewed in the context of organometellic catalysis k4 2.
General Results Several decamethy3metallocenes
decamethglmetallceene
(2.1; M = V, Cr, Co, Iii) and
cations ((1.2;M = Cr, CO, Iii, n = 1; li = ici,
n = 2) have been prepared and their electronic properties studied. NMR, IR spectroscopy, magnetic susceptibility and, in some cases,
3 X-ray crystallography have b-en used to show that the compounds (2.1) and cations (2.2) were D5d or D5h with low-spin configurations. Reversible, one-electron redox reactions have been demonstrated by cyclic voltammetry for the systems:
where PI = Cr, Pi, Fe, Co, Ni
The decamethylmetallocenes were, in general, more easily oxidized $3 to the corresponding cations than were the free metallocenes. and I3C LNR and TJV spectra for several decamethylmetallocenes have . been recorded [7]. r
0
Q 0
2.1
-iT 0
ti M
n+
I
M
1~ 0
2.2
Several complexes of pentakis(methoxycarbonyl)cyclopentadiene, HCS(C02He)5, have been reported. The fully-substituted metallocenes (2.3; PI = Mn, Fe, Co, Ni; R = C02Me) were obtained by treatment of the free ligand with the appropriate metal(I1) acetate. The complexes (2.3) are water soluble and are fully ionized in water. The structure of the ruthenium complex (2.4) has been determined by X-ray crystallography M. The frequencies and forms of the normal. vibrations in symmetry coordinates have been calculated for the metallocenes (~-CSHS)~M, where 14 = i%g, Ca, V, Cr, Mn, Fe, Ru, OS, Hi.. The nature of the metal. exerted only a small influence on the shape of the normal vibrations. References
p. 128
Force constants for the vibration werecalculated [9].
4
CO We
R R
-:l‘r 0
R
R
R
PI
R”
Q 0
I 2
R
R
R
%. 3
2. 4
ryhe -I9 TT2' ..I&?spectra
of the 3- and 4-fluorophengl derivatives of ferrocene, ruthenocene and osmocene were recorded. 'TheTaft equation was used to obtain inductive substituent constants of -0.032,
-O.Qi+Z and O.i\& and reSonance Substltuent constants of
-0.107,
-0.0?7
and 0.095 respectively for the metallocenyl groups.
The fluorophengl derivatives of tricarbonyl(y-cyclopentadienyl)manganese and -rhenium were prepared also and examined [IO]. The cross polarization method has been used to obtain highresolution solid-state '31:323 spectra of fcrrocerie, ruthenocene, biS(r,-benzene)chromium and related sandwich compounis. The shieldin,-,tensor anisotropy reflected the character of the bonding. Xotion was observed in Several of the compounds and has boen used to
assign the shieldinS tensor principal directions
Cl'l* The dynamics of ring rotati.on in ferrocone, nfckelocene and
ruthenocene have been studied by incoherent quasi-elastic neutron scattering.
At temperatures above the 164'K phase transition the
activation energy for ring rotation in ferrocene fell to
0.5 kJ mol-’
T.4 2
(approximately half the lori temperature value).
At
room temperature the n,-cyclopentadienyl rings in nicirelocene behaved the same as in f'errocene but in ruthenocerie they reoriented l.eSS frequently and resembled those of ferrocene below 16b OK [12]. The proton af'finities for twenty organotransition metal complexes including benchrotrene, methylcymantrene, ferrocene, ruthenocene and nickelocene have been determined in the gas phase by ion cyclotron r:>Sonance spectroscopy. The site or protoaation has been determined in several. cases [131*
5
~~icrosolution optical spectroscopy has been used to monitor the fate
of
metal atoms deposited into cryogenic solutions.
i'h0
interactions or iron, cobalt, nickel and zirconium vapours with liganda such as COD and toluene were examined and reaction intermediates proposed on the basis of the optical spectra obtained [14]. A theoretical study using ISit SCF EO calculations has been carried out in order to make comparisons between the cyclopentadienyl, borabenzene and benzene ligands in sandwich complexes of chromium, manganese and iron. Ground state differences were found within both the borabenzene series and cyclopentadienyl series of complexes and also between th.e two series.
The differences
were rationalized in terms of a simple ligand field model
[Is].
The Thouless instability conditions in a series of polydecker organometallic sandwich compounds have been investigated by semiempirical IliDO calculations. Hartree-Pock fluctuations of the singlet, non-singlet and non-realtype were found. The PeaSOns for the various instability conditions vere analyzed [I61. 3.
w@~lv(co~ic The solid state structure OS the (y-cyclopentadienyl)vanadium
complex (3.1) has been determined by X-ray crystallography. In solution, IR, 31P and " V NM3 spectroscopy showed that the molecule was fluxionaf down to 200 OK [17]. The photoreactions between tetracarbonyl(?-cyclopentadienyl)vanadium and the ligands
Ph2iGB2&Ph2 (6 = P, As, Sb) have been
investigated. The complexes (3.2 and 3.3; & = P, As, Sb) were isolated and investigated by 51V XhR . The crystal and molecular
3.1
References p. 128
6
myJ \ Ph$TX2EPh2
3.2
3.3
was determined by X-ray analysis structure of (?-Cj:'~)V("O)?ns2Ph4~
bl.
The binuclear dkradical (3.i~)was obtained by coupling of bis(v-benzene)vanadium,
the product was characterized by 3H
spectroscopy [193.
3.4
The condensation of chromium vapour with phenyl- OF Q-tolylferrocene produced l;he bis(n,-arene)chromium complexes (,$.I;ii = il or Ke) respectively
[Xl].
Fe
Cr
Fe Ph
LL.2
4.1
Treatment of hexacarbonylchromium with I-phenyl isophosnhinoline produced the bis(tricarbonyl_chromium) complex (4.2) [Zl]. Reaction of tricarbonyltris(methy1 cyanide)metal complexes with 4-R-X3-arsenines and 2-aryl-4-R-X3-arsenines gave the corresponding tricarbonylmetal complexes (it.3;R = Ph, cyclohexyl, t-Bu, Et) and
(4.4; R = Ph, cyclohexyl, t-2;~; &I = Cr, ho, Si)[22].
The preparation of some oligomeric (y-arene)transition metal tricarbonyl complexes has been reported [2_1], Steroidal hormones containing benzene rings, such as estradiol, estrone-j-methyl ether and estrone have been treated with chromium, molybdenum and tungsten hexacarbonyls to form the tricarbonylmetal complexes, such as the tricarbonylchromium complex (4.5). kinetics of formation was monitored
'The
[24].
Benchrotrene and related complexes (4.6; ii. = Ii, l\le, N = Cr, NO,
W)
have
been
obtained in high yield by heating the free Ph
MO
umg
ti
MN3
4.4
Referencesp.128
OH
4.5
ligand
with
ii.6
the appropriate
the autoclave
with
The synthesis derivatives
hexacarbonyl
reported. induced
.i“hemultistep
achieved
by using
carbonyl
groups.
The corresnonding
complexes
The reaction chromliium produced products
Cr
4.7
reaction
for replacement
labelled
was
of' the three
thiocarbonyl
X = S, Se) wel'e obtained
of trivhenylbismuth the lT-complexes (4.8, !;.9
with
and in similar
triamminetricarbonyl-
(q.8, 4.9 and 4.10;
and 4.10;
(=+
7 (140)
'C in
[%6].
reactions
Similar
(Ll.7;
excnange
atom >0 13 C enrichment
and>90
13 CO as the reagent
selenocarbonyl
at 150-170
picoline or thiophene catalyst [&I. of 13 CO labelled benchrotrene and benchrotrene
has been
was photochemically
metal
a pyridine,
lWh2
Cr 2
cx
NW3
4.8
PI = Bi).
1~~= Sb) were obtained
4.9
by
4.10
treatment of the chromium complex with triphenylantimony in the presence of boric acid [27]. 4.
(ii) Spectroscopfc and Physico-chemical Studies
The crystal and mo3.ecular structure of the (r\-naphthalenefchromium complex (4.11) has been determined by X-ray crystallography. The molecule exhibited an octahedral. arrangement about chromium and Cr-naphthalene bond distances were similar to those found in the corresponding tricarbonyl complex. The structure of a related (~-phenant~rene)chromi~ complex was also
had a short Cr-P bond.
reported [28].
The crystal and molecular structures of hexaethy~benzene and of its tricarbonylchromium, tricarbonylmolybdenum and dicarbonyl(triphenylphosphine)chromium complexes have been determined by The structure of the tr~pheny~phosp~~ne complex
X-ray analysis.
References p, 128
10
differed from the others in that all six of the ethyl groups were arranged such that the methyl moiety projected towards the uncomplexed side of the ring and the molecule assumed a staggered conformation [293. The crystal and molecular structure of the dicarbonyltrifluorophosphinechromium complex (4.12) has been determined by0 X-ray crystallography.
The chromium-phosphorus distance, 2.132 A
was the shortest found to date and suggested that the trifluorophosphine ligand was a good ?r-electron acceptor [30]. The structure of the tricarbonylchromium complex (4.13) has been determined by X-ray analysis. In the lattice the mo1ecuI.e was distorted in that one of the Cr(C0)
3
groups could be on either The geometry
side of the phenyl ring to which it was bonded.
around the tin atom was approximately tetrahedral
4.13
[31].
4.14
X-ray crystallography and NIviRspectroscopy have provided strong evidence that the fl-phosphorin)chromium complexes (4.14; R' = Ph, CHe3; R2, R 3 = Ke, Et, CIVie UMe, %2t2, 5')have a 3' zwitterionic structure [32]. The benchrotrene complexes (4.15; X = E-He, o-Pie, e-OMe, p-F, E-CI and 4.16; R = O-Me, E-he) have been prepared and the IR and 'I-i WR spectra recorded and interpreted. Substituents in the uncomplexed benzene ring in complex (4.15) had little effect on the stretching frequencies of the tricarbonylchromium group. Some electron delocalization between the two arene rings was indic;;ed by the NKR spectra (331. MO NIIE spectra of LYIo(CO)~ complexes (L = I-cycloheptatriene, ?-mesitylene, q-o, m, and p-xylene, l-toluene, n,-cyclopentadienyl) have been recorded and discussed. The chemical shift was related
(CO$
4.16
4.15
to
HI@ m~~ybd-m-m-z~~~~ AS part
of
nonequivalence
methyl
the
crystal
cation
characterized
with
with to
respect
g-Be,
J@3, been
the anion
E-O-Se, prepared
and investigated delocalization
References p.
to
interpret
The radical have
128
in has
S-He the
been
isopropyl
I$
pp;
potassium
unpaired
= Ii;
cations, of
the
by
X-ray
units
group.
of
gauchewere
[?$I. (4.18;
R’
= H,
R2 = +*-he,
j.@3
the
cOW?lexes
The results density
or
The results
R3 = H,
reduction
benckro-
were
trails-gauche
colnplexes
electron
magnetic
structure
MM? shifts
bsnchrotrene
by
of
determined
either
diastereotopic
j+l,
origin
eonformation&.
g;roup
bY !.ISR spectroscopy. of
the
iso-propylsulphonium
and molecular 14.17)
the
[3i;j.
into
groups
Two alternating
crystaifography,
used
S~XWI~~~
an investigation of
tre~esul~honi~
gauche
bond
over
parent
f
confirmed the
ligand
system
12
0
R
COCH,CH2CH3 i
p Cr
w3
m3
4.19
4.20
Dipole determined
moments
and molar
for a number
Lerr
of benchrotrene
C OPle, CO2ILle,Oi,Te,iTEz, 1;HIze,ilKe2). evidence
from
conformations plexes
(!+.liJ)and t'ne free
In the mass
spectrum
hydro:;en transfer deuterium
processes
labelling
Iropylene
elimination random,
the decomposing from
ion.
0
occurred
Pm3
4.21
to_:ether ;;ith
that t.le .,,referred
complex
and these
goup
the com-
In another
(!.,.cC)several
were
studied
by
in the I-, 2- or j-position.
specific
on the pressure
(i:Aciaffe..'ty rearrallgerflent) of carbon mollO:~ide at
rearrangement
hydrogen
was
the I-posi.tion of the nro;oyI croup; to the ester spectra
of fL)ur '0e;icilrotre:le
(!1..21;PI = Cr, X = Okle, OBun,
x
C02he,
C02sun)
and of the
7 0
?Pi
(k.19; R = CHO,
results,
silmf.15rin both
[30 of the chromium
was either
depending
been
ligands
carbonyl c?rbon atom [36]. The electron impact mess complexes
were
of the "ropyl
or mainly
transferred
complexes
These
I;? sr:ect:-osc,o_-y indicated of the substituects
at 509 nm have
constants
Cr (COj3
4.22
4.23
R
13 analogous tungsten complexes (i&.21;PI = w, x = Op;;e, oaun, COpBun) have been recorded and analysed in detail to give complete
CO b& 2
fragmentation diagrams.
Differences between the tungsten and chromium complexes were attributed to the stronger electpophilic character of tungsten and its tendency to attain higher oxidation states [39]. The mass
Spectra
of negative ions formed by the dissociative
electron capture (Jd,'c) Of I-complexes have been recorded and interpreted. Ampg the complexes ezamined were (q'-benzene)-, (q6-indene)-, (n,-fluorene)- and (7 -azafluorene)-tricarbonylchromium. 'The[A-H]' ion from (\6 -indene)tricarbonylchromium underwent a process of recoordination of the chromium atom from the benzene to the cyclopentadienyl ring [40]. I"iassspectra of the benchrotrene negative ions (4.22; X = R, Cl, F, I, Otie, ;JKe2) obtained by DtiC have been obtained. 'The first maxima of the resonance of the ions [h-CO]- was shown to have a linear dependence on the Hammett CP constants [41]. The favoured conformations in the gas phase of several L = CO; benchrotrenes such as [4.23; R = CO$ie, CH(CNej)2, COI'ie, method and R = C02Me, L = CS]have been determined by the A:R,L compared with solid state conformations obtained bY X-ray crystallography.
The conformations were similar in most cases
[42 3. Kinetic
isotope effects have been determined for the sodium
borohydride and sodium borodeuteride reduction of (?-indanone)tricarbonylchromium complexes (4.24) with substituents on carbons = 2.46 was found cghenR1 = H, 2 and 3. The maximum effect &/kD R2 = exe-tie and this corresponded to a shift of the transition R2
0
RI
0
P+ Cr (co)3
4.24
References
p.
128
14 state from hindrance
a late
to an early
position
by increased
steric
[lc3].
_$:~ro~~en-dcuteriwriiexchan[Je in the benchrotreiie carn;)lexes
(1$.:‘3;
R z B,
Lr = PPh3,
ferrocenylPPh2,
.
Rate
constants
demonstrated ligcnd basic
!%Iasa stroqer media.
the complexes
electron
Only a small (I;. i3;
CO) has be,:~.studied
that
donor
in
determilled f'or exchange the farrocenylPPh
2 the PPh_ ligand in 3 in the exci?an,,erates for
than
difference
l? = H, L = ferrocenylPFh;J,
CO) were
observed
[4 3. Rydrogen-deuterium
(ir..23;
exchange
in the bcnchrotrene
complexes
11 = Ph, PhCH,,
PhCH.CIi,, PhCO, PhO, L = CO, PIh3) in 2 stvdied and rate constants obtained. 111 i;he
Cb'3C022 has been complexes
(!+.Tj; L = PPh
no effect
on t‘ne rate
reaction
positions
)
the
in the free binuclear
in
L = PPh3) had “he
3
the
coordinated
similar
reduction
chaq;e
in ring
areL?es. ligands
reactivities
The _ o- , m-,
(;1..23;
[hi].
of
Jotassium
borohyaride
r>ro;;anolor methanol ii. iso-,,
or
gave
the corres ,onding endo-alcohols
(4.26).
R4
NaBH,,/i-C,H,OH iG3H4/CH30H/H20
-
Cr CO'~'CO co
4.25
to the same n2d E-
for the complexes
by sodium only
substituei.t inad
of excl?an(:e, in ohars contrast
4.26
I’he [email protected]
15
w C02H
0
0
R
CP
Cr
(CO+
4.27
(cO)3
4.28
0
4% Oo
0
CP
CP
(COj3
hm3
4.29
ligand was removed auantitatively from these complexes to give cis- and trans-indanols [461.
The
optically active diphenic acid complexes (+)-(4.27;
R = H, I%) and (-j-(4.28;
R = C02H) have been obtained by resolution
using the cinchonidinium salts although enantiomeric purities were R = CHO) underwent kinetic resolution only G8$. The aldehyde (4.28; with a chiral lithium aluminium hydride complex to give the aldehyde (+I-(4.28; R = CHO), the alcohol (-)-(4.28; R = CH2OH) and the lactone (4.29). The optical yield was 33%. The CO spectra of the optically active products were obtained and used to assign the chirality by comparison with benchrotrene complexes Of known absolute configuration [471* The methoxybenchrotrene complex (4.30) underwent regiospecific lithiation at the k-position and then electrophilic substitution References
p. 128
16 with
cer'oon dioxide
the Li-substituted reactions
to give,
arene
:~rererzoorted
after
(q.jl)
in 91% yield.
4.31
(iii) General
Chemistry
'The electrochemical complexes (4.32; 2 R = He, Okie, 2)
oxiJation
of the tricarbonylcnror~iurn
I?’ = ,,3 = pJ, iI2 = ii, OPie, and (1~.33; .?I = ft3 = Iale,
7 R” = Sikre ) gave stable cations on the cyclic 3 Oxidation of the mono-cor~~>lc.;~:sl4.33) SCale. while
the bis-complexes
stability electron phengl
of the cations
(h~.j:j)gj,avestahlo rias increased
= H, voitametric
gave
time
stable
dications.
cations
i'he
by the introiluction of
dona.tinp; ;;rsoupsinto the (?,Q and 6 !,ositio:.s of the
rings
A series isocyanide
..ieve:qal r>olated
[IJ.~].
4.30
4-
demetalrtiorr ar:d methylation
[1_1_9]. of chromium
li~;ands (j+. 34;
complexes R1 = CO,p,
containin:; functionalised Oi,re,rule,22,
CfDre,, CIsre3, .~
1ccn
)
MeOH UV
Scheme 4.1
4.35
WI"ie2,R2 = 0, no, E-W, 0, E-pie, R3 = Ph, FlNe2, O&t, SEt) has been prepared (Scheme 4.1). The manganese complex (1~~3.5)was prepared similarly.
Infrared and mass suectroscopic studies showed that
the Presence of a carbonyl group M to the nitrogen resulted in the ligand being a better electron acceptor than CO [$I]. Ultraviolet irradiation of the tricarbonylchromium complexes [k.36; n = m = 0; n = 2(2,3-Ne2), m = 1,2; n = 3(2,4,6-b&3), m = 2,3]induced intramolecular cyclization to produce the corresponding dioarbonylchromium compounds (4.37') [sl]. Rj
=
Irradiation of the tricarbonylchromi~ complexes (4.38; = H3 zz H, file; I$ = Rz = Ne, R3 = CK20W, CH,CH,OH) with
$
CR2=CRCRR40R5
(where R4 = H, CH2CH2Ph; Rs = H or allyl) gave the
correspondzing cationic ~-al~y~chromi~ complexes (4.39) [sz]* uv irradiation of benchrotrene with ally1 alcohol and its derivatives in the presence of hydrofluoroboric acid gave
References p. 128
18
Men
9-
(CH2 lrn7
(CO)
F-2
cr./
(CO) 2
3
c /
He
4.36
4.37
(v-erene) (q-allyl)chromium l,j,s-Me3, were
3,5-Me2,
obtained
cationic
compleses
(ib.!~G;;I1 = OH, H,
Cfi2OH; R2 = H, CI-:,iCli2Ph) , Similar
by cleavage
of chelate
dicnrbonylchromium
complexes complexes
such as the benchrotrene
(4.41) and by proton
cleavage
simultaneous
irradiation
of ally1
benc'nrotrenes
as the ether
(ic.42).
Several
substituted
related
reactions
were
with such
re:lorted
[531. A kinetic study of the reduction of the T-acetophenone complexes [I+.;'?; d = ':OPie,L = CO, CS, P(9Ne)3, P(OPh)3, PPh3 PBu3]by arene
of
sodium
borohydride
has been
ligand
>Jas controlled
carried
electronically
out.
, ,The reactivity
by the
Cr(ZO)2L
[54].
group
The rate chromium
b 0
of deprotonation
complex
(4.43)
of fluorene
by potassium R1
has been
-
+
R3 BF -
4
R2
Cr
mN3
4.38
and its tricarbonyl-
hydride
4.39
determined.
19
CH20CH2CH=CH2
CH2 \ 0 (C012Cr I / CH2=c~
4.40
4.41
/ CH
Cr 2
w3
4.42
'H and I3C spectra showed that for the anion generated at -20 'C the Cr(CO)3 group was bound to one of the benzene rings but when the anion was formed at room temperature the Cr(CO)3 group wss bound mainly to the cyclopentadienyl ring [5's].
Cr (co+
4.43
=H;
Treatment of the tricarbonylchromium complexes (4.44, R' = R2 R1 = H, R2 = Me ; R LR2- Pie) in dimethylsulphoxide with
potassium t-butoxide followed by condensation with an aldehyde R3CH0 CR3 = H, Ph) produced the corresponding alcohols (4.45).
The
strong electron withdrawing character of the Cr(COJ3 group had enhanced the reactivity of the benzylic position towards attack by the base [56]. The reaction of benchrotrenic ketones with Grignard reagents was studied.
References
p. 128
Nixtures of secondary and tertiary alcohols were
20
;i 7-
I
R'
0
9-
CH
0
1
RZ
Cr
Cr
(W3
wa3
IL.44
4.45
formed and a mechanism of the secondary metal
Cr
NoI
atom
was proposed
alcohols.
been
in hy:iroy;en transfer
ketallation
lithiated
to account
'This involved
The tricnrbonylchromium have
4.46
of the
[57]. (!;_.iiC,;
complexes
with n-butyllithium
of the substituted
for tile formation
participation
arene
at the --ortho-positior:. The lithiated a series of electronlliles ~8 .
‘i
=
if,
Oi?e, F, Cl)
at low temperatures.
complexes
occurred
intermediates
we?e
exclusively condensed
with
the tricarborlylchromium of ii:R(:ij)U!j" :;ith '
The rnaction complex after
(k.47)
oxidative
has been investigated. removal
i'he major
of the tricarbonylchromium
product group
obtained (Scheme 4.2)
CM
CH
I
3
LiCHCN
11.47
Scheme
4.2
21
corresponded
to
nucleophilic addition on an arene carbon atom
which was in an eclipsed position with respect to the carbonyl group of the Cr(CO)3 unit of the most stable conf'ormer[S9]. Treatment of tricarbonyl(~6-1-methylihdole)chromium with n-butyllithium-tetramethylethylenediatnine followed by ethylchloroformate produced the 2-ethoxycarbonyl substituted product (4.i48; R = C02Et) in good yield.
Lithiation of the Z-substituted indole
4.4%
complex (i+.48;
4.49
3 = SiILIe3) followed by condensation with ethylchloro-
formate afforded the 7-ethoxycarbonyl derivative (4.49)
2s
the major
product together with some tricarbonyl(\6-4-ethoxyycarbonyl-l-methyl2-trimethylsilylindole)chromium
k4 The reactions of (~-benzene)dicarbonyltriphenylphosphine-
chromium with aprotic acids, for example mercury(I1) and tin(IV) chloride, have been investigated. Complexes were formed at the chromium atom which was the position in the molecule with the
(MeIn
4.50
References p. 128
22
i'he II? s;)ectra of the czmy)lexes sho;red high
hi,ghest basicity. carbonyl
frequencies
'The chromium
[61].
complexes
(2,&,6-rle3)] h ave been
Cr(CO)j
of the corresponding
in ;:ood yields or
[q-l
triethylamine
c!ny ri-1;;
L = _ o-31' u6 H ii0) have (~;_.;land i_1_..52;
by the reaction
,j,~-~ie~CbH3CI:~CHZDE]Cr(CO)j folloyred by ultraviolet
:;ith Li'Cl aild
irradtation
reagerits gave
the chiral
n = 2, R = Ile, Bu; n = 3, 2 = he
4.53
[63].
4.5s
Treatmellt of the brid{;ed benchrotrene :rith alkyllithium
been
of [l-l,j,S(~uC~~,_~~H~)~CcHj]-
14.51
where
without
[62].
The chromi.uun complexes prepared
by treatment
(4.50; ;i = F, PhO) !%rithphcnyllitI;i~m
complexes cleavay;e
[i$.";O;Ii = l'h; n = 2 (_3,5-Lie,),n = 3
obtained
complexes amines
b41.
(ic.33; n = 2, 3)
Ph(CH‘~)ili,~rh,:fiPh,
23
Cr
(cOLj
4.5s
4.54
The reaction of benzylcarbenium ion with nitriles to give amides was facilitated by stabilization of the carbenium ion through complexation with the tricarbonylchromium group. Thus the (r\-benzylalcohol)chromium complex (14.54) was attacked by the nitriles, tiCN, where R = Ke, Pr, CW=CFi2, CH2C1, Ph, PhCHZ, 21v,e.C6H4,to give the corresponding amides (4.55) [65]. The charge-transfer comples formed between t;ricarbonyli7j[2.2]paracyclophene)chromium (4.56)
and
1,3,5-trinitrobenzene
in It was concluded that
1,2-dichloroethane has been investigated. there was direct interaction of the 1,3,5-trinitrobenzene with the chromium d orbital [66].
S
Ph
4,56
References pr 128
4.57
24
Senchrotrene
in ace';onitrile IJas attackeLi by 2 nitromethar,e to
lricarbol?yl-cllromium, molybdenum
and -tun;:ste:: Gor~ple;tes of . 1 -oxides have been o;;idizeu with
1 -alkyl-3,5'-diphScnylthiabenzene
IIO+PF6- in dichloromethane dicarbonylnitrosyl
at -76 'C to give
the cationic
[&.57; 1.1= Jr, iio, d,
complexes
CE(SiiGa3)2; T4 = Cr, ii = $ie, A,
CiI,,CH;;lPh, JH,&Le
i? = ~.;(c;h’.P11). 2 ii
] [uo, 693.
i3enchrotre: es bearin,? one, twg or tnree'.metboxy _,rOU')SOil the b.,nzene ring of
methyl
were
sorbate
Y'he reaction of an
effective
to methyl of furan
deac:ivated occurred
with
after
twelve
hours
as the major
:',!J,b-triphenyltriazine
insignificant
compounds
were
(5.1 ),
In a similar amounts
isolated
The structures
produced
was virtually
chromi'um vapour
product
reaction of cationic
together
gave bis(r\-
~itn
some
by cyclotrimerization of bromobenzene
of
;-Jithchromium
bis(?-arelie)chro:-Lila
[??I.
of bis[y-I,&-(trifluoromcthyl)benzer:e chro;Lum 3 heve been
(t:ifluorom~~thyl)benzene]chromium
1
with
formed
bis(y-1,3-(trifluoromethyl)benzene
‘> .
as catalyst
,Tliocatalyst
and up to 150 a1;cylatj.W: events
of benzonitrile
benzo~itrile)ckromil~
in the l)resence
[711*
per molgbde:,um atom
benzonitrile.
compound
and %,5-di-t-butylfuran.
The reaction
only
[TO]. t-butyl chloride
(y-2rene)tricarbonylmolybdenum
z-.t-butylfuran
for ',:henyCPOge:!ctiOn
catalysts
hexenoate
5.2
3chromium, and bis[q-l-cnloro-jdetermilled by A-ray
25 analysis.
The results suggested that the CP3 group did not behave
as a strongly C-electron-withdrawing group and that the polar effect of CF was a "through space" rather than a "through t'nebond" effect [73].3 The heats of thermal decomposition and iodination for the bis-(q-benzene) complexes (5.2; M = No, W) have been determined
+
by microcalorimetry in the temperature range 520-523 OK.
'The standard enthalpies of formation at 25 'C were obtained as 235.3 and 2'42.2kJ mol-' for the complexes (5.2; M = No, W) respectively. Netal-ligand mean bond dissociation enthalpies were derived as 247.0 and 304.0 kJ mol-' for benzene and toluene respectively [74]. Hindered rotation about the metal-ligand bond in the chromium complex (5.3)
spectroscopy has been studied bylH and 13C Zl\iR
9 0 -6-c 6 0
0
Cr
0
5.3
[75].
Cr
0
2
5.4
The redox reactions of twenty bis(?-arene)chromiu
complexes
have been studied via the rotating disc electrode technioue in dimethylsulphoxide.
The half-leave potentials correlated well
with the meta-substituent constants.
It was concluded that the
electronic effects of the substituents were largely transferred to the metal atom by an inductive mechanism
[741. Bis(I-ethylbenzene)chromium has been treated with hydrogen
peroxide in ether or methanol. A yellow solid was isolated and ESR spectroscopy showed that there were peroxide linkages present [771. Bis(r\-benzene)chromium was oxidized by treatment with bis[tris(pentafluorophenyl)germyl] mercury in glyme to give the salt (5.4) in 95% yield [78]. The lithiation of bis(n\-benzene)chromium followed by treatment with dimethyldisulphide gave the r\-methyltlniobenzenederivatives References
p. 128
26
(5.5;
R = Ii
and S&e).
derivatives
and
T‘ne reaction with
The -SH spectra of the r\-methylt:iiobenzene corresponding radical cations were determined.
their
of bis(\-methylthiobenzene)chromiuim
tctracarbonyl(q-norbornadiene)molybdenum
reolacement
product
interconversion
0
(5.6) which
at room
ra:!icico:~formationaI
[791*
(I> / 6 SMe
R
0
i>
The
0
self-exchan{;e
(?6-arene),Cr/
rates
have been
measured
technique.
Cyclic
It was concluded
transition densities
state.
accounted The
of
the electron
mechanism
oligomerization
activity
of the chromium
in the exchange
the electron ei'fects and rates
[oo].
in the presence diphenyl,
as catalysts
has been
and two defluorotrimcrs
were
'The relative
order
of oligomers. complexes
was:
>bis(q-bil,henyl)-
has been used
of perfluoropropylene
of
bis(r\-I ,3,5-trimethyl-
>bis(q-benzene)chromium
Bis(?-benzene)chromium
proceeded
( arene = bonzene,
>bis(q-hexamethylbenzenejchromium
oligomerization
that
by inductive
hexamethylbenzene) trimers
in the mixture
benzene)chromium chromium
Dimers,
t'ne one-
complexes.
reactions
of perfluoropropylene complexes
line broadening
by the side to side
indicated
affected
for the variations
l,j,S-trimethylbenzene,
identified
exchange
and probably
were
= toluene,
to investigate
[($-arehe),Cr]+
All the results
chromium
in the
and chlorobenzene)
spin resonance
of a series
of bis(y-arene)chromiu
investigated.
(where arene
b:as used
that
parameters
ethylbenzoate
voltammetry
sphere
about
systems
biphenyl,
by an electron
reduction
by the outer
and activation
[(T6-arene)2Cr]i
methoxybenzene,
electron
Plot
SMe
SMe
benzene,
\
CP
Cr
these
underwent
temperature
(5.5; ;i = .5&e) ;;ave the li:,and
["I]. as a catalyst
to dimers
for the
and trimers.
One mole of the complex was effective in converting 50 mole of the monomer 6.
[82].
[(q-C+17)Cr(CO)3]+ and (C7R4)Cr(CO)3 Desilylation of the eycloheptatrienyl complex (6.1) produced
the binuclear cycloheptatriene complex (6.2; I4 = Cr) [83].
SiMe3
om3
6.1
6.2
Ultraviolet irradiation of tricarbonyl(y-1,3,$cycloheptatriene)ChrOmium with the monosubstituted fulvenes [6,3; R1 = H, R2 = OCOCH 3; R’ = H, R2 = W(Me)2] gave the corresponding dicarbonylchromium complexes in the exo- and endo- forms (6.4 and 6.5).
The disubstituted fulvenes (6.3; R' = R2 = ONe , R1R2 = -SCH CY S-, RI = Me, R2 = Pin)produced the corresponding dioarbonylckbsium
derivatives
(6.4).
A similar reaction with
cycloheptatr~enyl}chromi~ the f'ulvene C~~~=~I~~~e2 produced the {P,~complex (6.6), the product of hydride transfer from the cycloheptatriene to the nitrogen atom of the fulvene [s4 J. The crystal. and molecular structures of the (I-cycloheptatriene)molybdenum and -tungsten complexes (6.7; lip = NO, X = Te; )I = g, X = Se) together with the dimolybdenum complex, (?-C7"?)llio(r-SePh)3I~o(C0)3, have been determined by X-ray CrystallOgraPhY. Bond lengths and bond angles were reported [85]. Tellurium dioxide was sctivated by evaporation in a metal evaporator and treated with the molybdenum complex (6.8). Reaction occurred to produce the first Te02 insertion product (6.9; H = Te). Sulphur dioxide and selenium dioxide were inserted also into the molybdenum-carbon bond to give the dicarbonylmolybdenum complexes (6.9; I4 = s, se) [86]. References p. 128
28
6.3
6.L.i
cw R2
‘-_
?-
bm2
+
0 I
-
M
6.7
0 0
M02
\
(C0j2XPh
6.6
.-. 9 MO-MMe
NHN14e2
RI
6.5
6.8
0
r--7
0
w
No-PhO_-Me
6.9
29 The tropylium complexes (6.10; $1 = Cr, No, IJ)were coupled by treatment with carbonylmetallates, for example,
~(~-~~~~)~~~o(co)3~and [HB(CO)~]-, to give the corresponding bis(2,&,6-cycloheptatrien-I-gl) complexes (6.2; M = Cr, MO, W) [o7].
Jo
Q 0
M
um3
6.10
The manganesetricarbonyl complex (7.1) was formed from cyclooctatetraene and(PE~(C0)4]3. This dehydrogenative transannular ring closure Of cyclooctatetraene was rationalized in terms or a disrotatory eleetrocyclization of a cyclooctadienyl moiety
[GO].
7.3
7.2
7.3
In an investigation of the formation and thermolysis of tetramethyldiphosphine bridged carbonyl complexes the cymantrene derivative, (I-C~H~)~~(CO)(~-~~~~PPW~~)C~(C~)~, was obtained [69]. Some cyclopropane derivatives of cymantrene have been prepared from the corresponding pyrazoline complexes [90). Several reactions of the mixed cobalt-manganese complex (7.2) Phosphorus and sulphur ligands as reagents
have been reported.
gave methy~c~antrene
and a cobal% complex
[5X].
30
Bromo~langanesepe~tacarbony~ has been attacked by Z,4-pentadienyltrimethyltin in boiling TEF to form tr,icarbonyl(15-pentadienyl)manganese
(7.3) in 52)" yield.
This complex was an open
analogue of cymantrene, it decomposed KLowly in air in the solid state
[92]. (ii)
7.
Spectroscopic and Physico-chemical Studies
The crystal and molecular structure of cymar!trene has been reexamined by X-ray analysis.
,I'he results indicated some localized
C-C bonding rgith bond distances in the ring between I.400 and ? ,439 8. Vibrational studies on cymantrene :'lso supported a breakdo>m of the fivefold symmetry of the ring outside of the crystalline environment [933. The crystal and molecular structure of the cymantrene Schiff base complex (7.4) has been deternlined by X-ray crystallography and the absolute configuration confirmed as S, the kn and &l atoms were trans with respect to the plane of the cycIo:?entadienyl ring
[941*
7.4
7.5
Dimethyldiazomalonate combined with the TI;F complex of cymantrene,
(I-C&)Rn(CO)$%F,
to give the diazoalkane complex
(7.5). &Bay crystallography demonstrated that the complex contained a monodentate diazornalonate group bonded through the terminal nitrogen and with the diazo group bent at the central nitrogen [9.53. The crystal and molecular structure of the cymantrene analogue (7.6) has been determined by X-ray crystallography. Korbornadiene was coordinated to manganese in an exo configuration and was a two-electron donor. The manganese-bridgehead mothylene hydrogen distance was 2.97 A" and indicated a lack of CH+**Kn interaction Cyclooctatetraene attacked the cymantrene complex (7.7) to
[96J.
31
form the (y2-cyclooctatetraene)manganese complex (7.b) the structure of which has been determined by X-ray crystallography.
Analogous
0I 0
Mn---(oW2
\ I
H & H
7.6
compl.exes containing \2-oycloheptatrien% and y2-cycloocta-1, 3,6triene were also prepared 13973. The crystal and molecular structure of the (y-cyclopentadienyl)manganese complex (7.9) has been determined by X-rag
Q
Q 0\ /
0
0
I
ml
Mn-O 3
(W2
(OC)2 /
7.8
7.7
crystallography.
\
The metal atom was sandwiched between the y-CSHs
and the y-CsPH2. Ph3 rings [98]. Gas phase He I, He II and Mg Kocphotoelectron spectra have been recorded for the complexes r?-CgH5_n(CH3)n]M(C0)3 where n = 0, 1, !? and Iv!= En, Re, The influence of the methyl groups was monitored by the shirts in both COP% and
ionization energies.
The magnitudes of the valence ionization energy shifts were relativeIy vdenc8
large which indicated a considerable change in the electronic
References
p. 128
32
0
0
0
Cr
(CO)..CS
z
;: Mn
mp
.F'h
7.10
7.9
I.11
structure of these compounds. It was concluded that electronic effects were as important as steric ef-i'ectsin determining reactivity differences between substituted and unsubstituted q!-cyclopentadienyl complexes. It was concluded also that considerable rhenium to carbonyl Tback-bondin g occurred [99]. The Re I and He II valence photoelectron spectra of the complexes [~-C;I;5_n(C~-I~)n]I.ljll(:10)ZL where n = 1, 5 and L = CzHii, c3H6 have been recorded and interpreted.
It was found that the
ionizations and stability of the complexes were sensitive to the geometry changes that arose due to the introduction of the olefin. These distortions were associated with a lower carbon-carbon bond Strength and an increased metal-olefin bond strength through increased T-donor/T"-acceptor
interactions
[100].
Gas phase core electron binding energies were obtaLned by an X-ray photoelectron spectroscopic study of a series Of thiocarbonyl complexes which included the chromiUm and manganese compounds (7.10 and 7.11)* The binding energies of the metal atom and the carbonyl grouts was approximately constant when one of the carbonyl groups was replaced by a t;:iocarbonyl ::;roup. It was concluded that the electron distribution within the complex was 1arTely unaffected by the change in the ligand. The greater donor character of -the thiocarbonyl ligand being compensated for by an increase in back bonding [101]. The mass spectrometric fragmentation of thirteen monosubstituted (y-cyclopentadienyl)tricarbonylrhenium complexes has been examined.
33 In general the complexes underwent decarbonylation, dehydrogenation and breakdown of the cyclopentadienyl ring
[102].
The IR and Raman spectra of phosphacymantrene and dimethylphosphacymantrene and liquid states.
(7.12; R = H, Me) h ave been recorded in the solid The spectra of the corresponding deutero
complexes have also been obtained.
A complete vibrational assign-
ment has been made and has shown that the y-CqE4P ring was more electrophilic and a weakerT-electron
donor than the T\-C~H~ ring
[I033.
R
0
P
%R
mN3
7.12
7.
(iii)
General Chemistry
Caulton has reviewed the coordination chemistry of the manganese and rhenium fragments (I-C~H~)M(CO)~ [104]. Reaction of the dicarbonylmanganese complexes (7.13; R = H, Ne) with the stereochemically rigid diisocyanides (L-L) 1,3- and 1,4-
7.13
References
p. 128
7.14
34 diisocyanobenzene, !I,&'-diisocyenobiphenyl and 1+,4'-diisocyanodiphenylmethane afforded mixtures of oligomers of the type [(RC;.I!Li~nl;O)n(L-L)n_~l ]"'[PF6-], [IOS]. R
1 3
I~;ethylcymantreneunderwent addition with liittig reagents, 2 ? P=IJHR-, where K 1 = ICe, R ' = 1: = Le , to form A and 2' zz j$:t, R
the products
(7.14;
i?' =
Pie,
$
=
3;
2'
=
L'rt, A2
'Treatment of the chloromethyl derivative
=
he)
(7.15)
[106].
with
:laOCH2CSXi gave the dicarbonylmanganese complex (7.16).
A
similar
reaction ~2s used to prepare the cymantrenyl derivative (7.17) [107].
The Priedel-Crafts reaction on t-butyl derivatives of cymantrene has produced the ester
phe
(7.'?8).
structure
of
tine
CorniJlex
(7.16)
was confirmed by X-ray analysis bos]. Several cymantrenylthioketone complexes [7.19; H = Pie, i-‘h, ave been prepared by &IL = ;J(CO)s; 8 = Ph, i,L z im(C0)2(Tj-CsHS h
13
CH2Cl
;r 0
CH2\
9
/CR2
Mn (CO),
7.15
Mn Gil (CO)2
CH
7.16
Me
7.17
7.16
35
Mn
treating the cymantrenylthioketone with the appropriate metal carbonyl [109]. The thermally unstable nitrosyl complex (7.20; L = CO) underwent coupling in the presence of zinc amalgam to give the dimer [(~-C$i5)Nn(CC)i:O]*while with phosphines the derivatives [7.2O; L = PPhg, P(OPh)3, P(C H ) ] were obtained. By contrast, attack 6 11 3 with hard Lewis bases such as pyridine, dimethyl sulphoxide and acetone caused decomposition with the binuclear complex (7.21; X = I) as the only nitrosyl containing product. Other members of the same series (7.21; X = Br, Cl, GO*, Me, Et) were obtained by nucleophilic attack of X- on the cation Treatment of formylcymantrene with chloroform in the presence for example triethylbenzylI- -l ammonium chloride , produced w-cymantrenylglycolic acid IlllJ* of water and a phase transfer catalyst,
Mn NO.1.L
7.21
7.20
References
p.128
36
(CH,)n$Me3C1-
9-
SiHNeR'
0
Mn
(COJ3
7.23
7.22
SiMe-C
JCH2
!I
\R2
Q 0
Q
SiMe-
in
ml
(co)3
(co)3
The cymantrenylammonium been
prepared
with
trimothylamine.
surfactants
by treatment
was
hydrosilylation
investigated
have
salts
as cationic
of Speier's (7.24
catalyst
in yields
to Live
R1 = he,
and 7.25;
a mixture
Ph;
of lb-2250 and &-59yA
[113]. (7.26
of the corresponding
accompanied
7)
chlorides
R1 = Pie, Ph) were effective in the 2 where R = CLie20R, I-‘nyuroxy-
products
The benzylpyrazoles
reactions
mxonium
5,
alkyl
HC5CH2,
R2 = Ci+ie20H,I-hydroxycyclohexyl) respectively
n = 3,
[112].
of acetylenes
of the two isomeric
of these
(7.23;
in the presence
cyclohexyl,
(7.22;
chlorides
of the corresponding
The use
Cymantrenylsilanes
reaction
CH=CHR2
0
proceeded
and 7.27) have pyrazolines
via oxidation
by simultaneous
with
been prepared
of the pyrazoline
reduction
by
benzaldehyde.
I'hese
to ?yraZole
of the benzaldehyde
[II&].
37
I2
CH Ph 12
CH Ph
Mn (CO)3
7.26
7.27
FQ 00
BF -
4
ti
M
(W2PPh3
L
CO.NO.PPh
7.28
7.29
0 0
BFk-
Re
CO.NO.1
7.30
References
p. 128
7.31
3
38 Treatment of the q5 -indenyl complexes (7.28; hi = Mn, Re) with gave the corresponding salts (7.29; 15 = nn, tie), The indenyl ligand was removed from the complex (7.29; Pi = Nn) by
NO 3F 2
4
treatment with KX, where X = BP, I, CZJ, to give bin(LO)2PPh3X. In a similar reaction the treatment of the cation (7.30) with
potassium iodide or iodine produced the complex (7.31)
[IIS].
The triphenylgermanyl and triphenylsilyl substituted anions (7.32; M = Si, Ge) have been alkylated with methyl iodide and
Q 0
Mn-.
“I
Ph 1 3
“co
co
Ph3M CO
R
7.33
7.32
benzyl bromide to give the dicarbonylmanganese complexes (7.33; M = Si,Ge, R = Me, CH2Ph).
The 'H !WR spectra of the benzyl
derivatives showed a sharp singlet for the CH2 groups which indicated that carbonyls were arranged diagonally to one another assuming that the molecule had a square pyramidal geometry
CO
H I 2
Fe
7.34
7.35
[II61.
39
The metallocene analogues of phenylalanine, D,L-P-cymantrenyl alanine (7.34) and D,L-p-tricarbonyl(r\-cyclobutadienylalanine)iron (7.35) have been prepared Cais and Tirosh
[117].
have reported the preparation of the
manganese labelled phenobarbitone haptens (7.36 and 7.37) via (cymantrenylsulphonyl)acetic acid and 2-(cymantrenylsulphonyl)ethylamine respectively.
Atomic absorption spectroscopy was used
to determine manganese concentrations in buffered solutions of the metallohapten containing immunoassay concentrations of antiThe results indicated 4;" feasibility -1 range of quantitative detection of manganese in the 10 g ml
phenobarbitone antisera. [IIS].
Et
Ph 0
0
0
S02CH2CoNH(CH&NYNH
SOz(CH2)ZNHCOCH2NYNH 0
0
Mn
Mn
w3
(W3
7.37
7.36
-Cyclopentadienyl-, r\5-indenyl-and r\5-fluorenyl-tricarbonylmanganese have been shown to exhibit approximately the ssme reactivity towards photosubstitution of a carbonyl group by triphenylphosphine
[119].
Cymantrene and methylcymantrene have been subjected to Cymantrene gave the
photolysis in glassy matrices at 77 OK.
species (r\-C5HS)Mn(C0)2, (r\-C5HS)Mn(CO) and, when ethers were present, (y-C5HS)Mn(C0)2(ether) and (s\-C5HS)Mn(CO)(ether)2. Methylcymantrene gave similar species although both substrates Rather underwent slower photolysis than the d6 hexacarbonyls. similar
behaviour on photolysis was observed for the ComPlexes
(r\-C6H6)Cr(CO)3, (~-c~H~)M~(co)~cs, [~\-c~(cF~)~S(C~F~)]M~(CC)~ References p. 128
40 and (v-CsH5)Fe(C0)21
[IZO].
The photochemically generated THF complex (7.38)
has been
attacked by ally1 alcohol and the product subjected to prototrophic elimination of water with HPFo-Ac20 to form the cationic (q-allyl)manganese complex (7.39). were formed in the same way
Several methJilated derivatives
[IZI].
9 0
Mn
(co)~THF
7.38
7.39
Irradiation of cymantrene with (q-C5H5CrSCMe3)2S produced the complex (7.40) and the structure of this molecule was determined by X-ray analysis [122]. Irradiation of methylcymantrene with diphenylsilane gave the dicarbonylmanganese complex (7.41;
X = H).
Treatment of this
CMe CMe3 I
3l
I (CO),Ph
Pin(CO)2H
b I
0
7.40
7.41
SiXPh2
41 complex with [Ph3C]BF4 in dichloromethane or with carbon tetrachloride in the presence of phosphorus(V) chloride gave the halogen derivatives (7.41;
X = F and Cl) respectively.
Reaction
of the latter complexes with carbon monoxide under pressure led to methylcymantrene silane
and the corresponding monohalogenodiphenyl-
[123].
Reaction of lithiocymantrene with the quinone (7.42) produced the alcohol (7.43)
which was reduced with zinc-hydrochloric acid
to give the corresponding phenol (7.44).
Oxidation of this
phenol gave the tricarbonylmanganese radical complex (7.45).
A
similar series of reactions was performed starting from lithiobenchrotrene
[124]. Lithiation of (dimethylamino)methylcymantrene using n-butyl-
lithium at -70 'C gave the lithio intermediate (7.46;
7.42
7.44
References P. 128
7.43
7.45
X = Li)
42
and this was treated with deuterium oxide, dimethyl~orm~ide
and
chlorodiphenylphosphine
to form the 1,2-disubstituted cymantreaes Hydroxymcthylcymantrene X = D, CHO, PPh2) respectively.
(7.46;
underwent similar metallation and attack by electrophilic reagents to form 2-substituted derivatives while diphenylphosphinocymantrene
gave
1,3-disubstituted
products under similar conditions.
The orientatjon of the reactions was confirmed by chemical methods spectroscopy and by IH and 13C lYI"IR
[125].
Mn 7.47
7.46
The cymantrenylchLoroacety1
complex
(~-C~~~.GCCH,C1)~(COf3,
has been treated with the sodio complexes, NaM(CO)n(?-CSHS), where M = Fe, W, No and n = 2, 3 to form the ci-motallated ketones f-7.47;
H = Fe,
w, Mo,
~%thy~c~a~t~ene
n = 2,
3)
[?263.
(7.48) u~der~~e~t ligand exchange with methyl
substituted Senzenes in the presence of aluminium Chloride to forum
7.48
7.49
43
the cations (7.49; arene = benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, durene, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene) [127, 1281. UV irradiation of tricarbonyl(r\-pyrrolyl)manganese with the metal carbonyls complexes (7.50)
M(CO)5
(coj3
7.50
Metallation of (T-pyrrolyl)manganesetricarbonyl (7.51) with n-butyllithium and subsequent quenching with D20 gave a trinucl,ear complex (7.52) formed by attack of the metallating agent at a carbonyl group.
Deuterium was not taken up into the product
(7.52), the molecular structure of which was determined by X-ray crystallography [I301. Picric acid attacked (y-pyrrolyl)manganesetricarbonyl
7.52
7.51
References
p. 128
(7.51)
44
NO
\2
7.54
7.53
to form which
a binuclear
has been
complex
determined
The kinetics
(7.53) the molecular
by X-ray
of nucleophilic
(7-b enzene)tricarbonylmanganese neutral
species
overall
rate
crystallography attack
cation,
to that for anion
addition
>CW-
dimethylforrnamide
at -10 'C to give of this product lithium
aluminium
on the
to give the corresponding investigated.
was unusual
to free carbeniwn
ions
b32]. has been treated
in THF at -70 'C and then ammonium
the formal
(7.55) were hydride
derivative described
(7.55;).
Several
includintJ reduction
to the corresponding
The
and it was similar
Tricarbonyl(q\-lithiocyclopentadlenyl)rhenium with
of
[131).
by anions
(7.54; X = X3, OH, CR), were
trend I??- >>OH-
structure
methanol
chloride reactions with
derivative
[133].
Q
CHO
0
Re
Re
co)y
w3
7.55
7,56
PPh 3’ Cl
7.37
45 Chlorination of the rhenium complex (7.56) with chlorine or thionyl chloride produced the salt (7.57).
Similar reactions
were carried out with tricarbonyl(\-cyclopentadienyl)rhenium The dicarbonylhydridorhenium complexes [7.58; X = SiPh3, Si(CH2Ph)3, SiPh,H] h ave been prepared by ultraviolet irradiation of
tricarbonyl(?-cyclopentadienyl)rhenium
silane.
The hydrides
with the appropriate
(7.58; X = SiPh3, GeC13, GeBr3, SnC13) were
obtained by protonation of the corresponding anions (7.59)
Re-H
[135].
Re
(CN2X
(co)2x
7.58
7.59
The hydrolysis and methanolysis of the manganese and rhenium complexes [7.60; R = H
Me Ph., L1L2 = (CO)2, (co)(Pst3), (CO) (PPh3), Ph2PCH2CH2;Ph2'] and (7.61) have been studied.
The
carbenium ions generated in these reactions were stabilized better by phosphine ligands than by the carbonyl group on manganese. The stabilizing abilities of manganese and rhenium were the same [136].
7.60
References
p. 128
7.61
46
.
(iv) Applications 3N-Methylcymantrene,
orally administered to rats, was efficiently absorbed, metabolized and excreted in the urine as the alcohol (7.62; R = CH2OH) and as the carboxylic acid (7.62; R = COZH).
In vitro, the same complex was metabolized by rat liver microsomes by a cytochrome P 4SO-dependent process [137].
Mn (W3
7.62
The toxicity of methylcymantrene in rats has been investigated.
The LDSO dose was 50 mg/kg for oral administration and
23 mg/kg for i.p. administration. Histological examination of rats treated with methylcymantrene revealed pathological changes in the lungs, liver and kidney.
Phenobarbital pretreatment protected rats from the lethal effects of 2.5 times the LD dose Polymer-bounddinitrogen complexes were prepared by treating vinylpyrrolidinone-tricarbonyl(~-vinylmethylcyclopentadienyl)manganese-styrene atmospheres).
copolymers with nitrogen under pressure (3
These dinitrogen complexes were more stable than
the corresponding monomer model dicarbonyldinitrogen
(?-methyl-
cyclopentadienyl)manganese
[I39-J No significant chain transfer was observed on polymerization
of styrene in the presence of cymantrene or poly(?'-vinylcylopentadienyl)tricarbonylmanganese [140]. Cymantrene has been incorporated with advantage into a fire extinguishing composition [141]. Extensive fleet trials of methylcymantrene as a gasoline antiknock additive have been subjected to statistical analysis in order to provide mathematical models for the effect of the
47
additive.
Hydrocarbon emissions increased linearly with additive
concentration while catalyst converter efficiency was increased in the presence of methylcymantrene
[142].
Methylcymantrene has been determined at ng/m3 concentrations in air. The sample was trapped in a small segment of a gas chromatography column and measured by gas chromatography using an electrothermal atomic absorption spectrometry detector.
The
limit of detection was found to be 0.05 ng/m3 [143]. 8.
Polynuclear (n-C$15)Mn(CO)3 Complexes
The THF derivative of cymantrene, (1-C5HS)~(C0)2(OC4Hs) combined with COS and COSe to form the binuclear complexes (8.1; X =
S,
Se).
An X-ray crystallographic investigation of the
sulphur compound (8.1;
X = S)
confirmed that the molecule was
centrosymmetric with a planar MI-I-S-S-WIunit
Mn-X
c-s-Mn
-x-Mn
8.2
8.1
The
I3 C
[IQ.].
IW3 spectra of cymantrenylphenylthioketone
binuclear complex (8.2)
and the The
have been recorded and interpreted.
structure of the complex (8.2)
was determined by X-ray analysis
[I45 J. The electronic structure of the cluster complex/4-CH2-[(yCgH5)"n(CO)& h as been investigated by vapour-phase photoelectron spectroscopy and by quantum mechanical calculations. The molecular orbitals used in formation of the cyclic Mn-CH2-Mn bridge were discussed [146, 1471. The crystal and molecular structure of the same complex has been determined by X-ray The molecule contains two trans-(l-C5HS)ph(CC)2
crystallography. References p. 128
48
r~roups joined by a bri:Qing methglene g;roup. rho maii~;acesemanganese interatomic distance was L.799 a [l&ii]* Tile Hc I r>iiotoelcctrons~sectrum ir; the ioniza.tion enorgy complex {o._3) range below 11 ev has been recorded for tile tzidjg3d
and cornpared with the spectra of methylcymantrene and It was concluded tilnt ttx?liul-Pin bond (~-C4"'"4"e)Mn(C0)2(~-C;?IIIC~, in (P.3) was an important factor i:l the stability of this compound [?tq. The irradiation of cymantsene with HECC02Pie in tetPahYdrofuran gave the dicarbonylmanganese derivatives (8.4 and ij.5) as the major products. Treatment of the manganese complex (8.4) with hydrogen chloride produced the corresponding q-olefin derivative (i-,.6)[1503.
(2 0
Q III
//JCH2\w,
Nn
0
c co
Pin
Me
2
IQl---
OX),
(CO)*
8.h.
6.3
Q 0
Pin-
(CO)2
CECl
8.6
CH
49
ma2 Mn=Ge=
Mn
a.7
8.8
Treatment of the hydride K[(r\-WeC5H4)Pii(CO)2GeH3]with acetic acid gave the trinuclear complex (8.7) which has been characterized by X-ray crystallography. The molecule is centrosymmetric and contains a linear Nn=Ge=Nn moiety with Mn-Ge double bonds. Treatment of the same hydride with mercury(I1) gave the trimanganese germanium complex (8.8) which contained a I??-Ge double bond in addition to a triangular Mn2Ge ring [ISI]. Reaction of methylcymantrene with GeH3K gave the potassium salt (8.9) which when treated with germanium tetrachloride produced the neutral complex (8. IO) [152].
Treatment of the salt
(8.9) with mercury(I1) chloride gave the tetramercury derivative (8.11) [153].
Q 0
Mn
(C0)2GeH3
8.9
References
p. 128
8.10
8.11
9.
Carbene and Carbyne (I\-C~~I~)M~(CO)~
Complexes
The methylpropiolate complex (9.1) was attacked by organolithium compounds, RLi, where R = Me, But, Ph, to give the carbene complex (9.2) in 50% yield [154]. Treatment of the methylcymantrene complex (9.3) with Me03SF gave the phosphorylid-carbene complex (9.4; R = H) and then the salt (9.5) in the presence of an excess of Me0 SF. The product 3 (9.5) was attacked by Me3P=CH2 to give the phosphorylid-carbene complex (9.4; R = Me) [li;S]. The reaction of dicarbonyl(q-methylcyclopentadienyl)-
C02Me I
Q 0
&-_
Mn-
--
(W2
(W2
9.1
9.2
\
C02Me
51
I
Q (0z$L?Me3 0
PMe + 4
OM6
9*3
9.4
FSO 3
9.5 (dior~~y~allenylidena)mang~esa
compounds with t-b~tyll~thi~
followed by protonation or methylation gave the vinylidene complexes (9.6; R = H, Me; and 9.7).
!!%a structure of the complex
(9.8) was determined by X-ray analysis lj%J* The carbene complex (9.9), obtained by treatment of Ph2C=M(CO)S with (y-CsH 5 )Mn(CO)$!RF, underwent photolysis to form tetraphenylethylene, diphenylmethane and 1,1,2,2-tetraphenylethane [1573* Treatment of the manganese complexes (9.10; R = C=CHCO2Me, T-CHZCCO~M~, C=C=CPh2) with nonacarbanyldiiron gave the corresponding tetracarbonyliron derivatives (9.11; R' = M, R2 = CO2Me; R' = CO Me R2 = B; R'R* = CPh2) [~583. 2 9 The electronic structures and bonding capabilities of the
References pa 128
101
P
tX
0
Fe
PF6-
PF6-
b 0
14.19
14.18
CN /
Fe
t?f+ 0
I
0 0
14.21
14.20
Q 0
Fe
+
Q
COR2
0
1
b0
J
14.22
References
p. 128
14.23
+
102 Reduction of the (T-benzene)(n,-cyclopentadienyl)iron cation (14.24; n = 1) with sodium amalgam gave the neutral complex (14.24; n = 0) in addition to the (v-cyclohexadienyl)iron complex (14.25) [2723.
a
Ph
P 0
n-t
;*-‘ 1 ‘._.
Ph
Fe
Fe
6
6 0
0
14.24
14.25
Electrochemical reduction
of the
( -arene)iron
cation
(14.26) gave successively the neutral rzdical (14.27) and the anion (14.28) which was attacked by iodobenzene and methyl iodide to
form
the (y-cyclohexadienyl)iron complexes (14.29; A = Ph, Pie).
273. , F 3 The electrochemical reduction of (7 -arene)(q'-cyclopentadienyl)iron cations in basic media has been studied. One-
Several related reactions were reported
electron reversible electroreduction occurred to give the corresponding radicals, that is the neutral 19 electron d7 complexes (?6-arene)(\6-C5H3)Fe(I). The behaviour of the radicals depended on the nature and the number of the substituents on the rings and also on the medium.
With all the radicals catalytic
reduction of the medium occurred together with radical dimerization or decomposition liberating Fe(O) or Fe(II) [274]. The (T-chlorobenzene)iron cation (14.30) has been reduced with sodium amalgam at -10 'C to give neutral (n,-chlorobenzene)(r\-cyclopentadienyl)iron which dimerized in air and in aqueous sodium borohydride
[275].
Hydrogen atom abstraction with oxygen from the neutral (T'-hexamethylbenzene)iron complex (14.31) gave the (n,5-benzyl)iron complex (14.32) which has been characterized by X-ray crystallography.
The exocyclic methylene is bent away from the
103
14.27
14.26
Q
Q
I-.
a’
R
0
‘._M
Fil
Fe
+ P 1 14.29
Cl
0
Fe
6 0
14.30
References p. 128
L
14.28
P 0
Fe
6
6 0
iron atom
and out of t:ie plane
(14.32) acted
complex metallic
t,
halides,
0
of the six-membered
as a nucleophile Ph2PC1,
PhCOCl,
Y-
14.33
14.32
14.31
CH2X
Fe
Fe
0
+
to organic
he3SiC1,
ring.
The
and organo-
hn(CO)jBr,
C H )Fe(CO)i2C1, to form the (l-arene)iron salts ['i&.33; ('i- 5 5 X = GOPh, PPh2, SiiGe?, r?ln(CO);, Fe(CO)~(~5,-C~KS), Y = Cl, Rr] , [2763. The peralkyl
$
= E; *I
reduction
of the corresponding
(;4.34) were
characterized
by spectroscopic (q-arene)iron
R1
(?&.jlb; RI
(t\-arene)iron complexes
= R'’ = Ne) have been obtained
1
to
compounds
complexes
of Fe(I)
The methylsted 5)
dimerize
R1 Men
M Fe
14.34
23 ,
The green
techniques.
(14.35; n =
Me,
amalgam
as d 7 19-electron
and magnetic
complexes
cations.
=
by sodium
14.35
thermally
105
at -20 'C through the arene ring.
The complexes (14.34
and
14.35) Were effective redox catalysts [277].
reaction with oxygen to give the corresponding q-cyclohexadlenyl complexes with doubly bonded exocyclic methylene groups.
FOP
example, (+$I$ Fe(l-C61vie6) produced the ?-cyclohexadienyl complex (lic.36). This latter complex underwent nucleophilic substitution with, for example, CB I, PhCOCl, Ke3SiC1, Ph2PC1 (~-CSHS)Fe(CO)2C1, (i~-Cg"~)No(C0)~?,I%A(CO)~B~, CP(GO)~ and nucleophilic addition with, f'or example, CO2, CS2 and
Q
,/--Qi 0
Fe
I
‘._.
CH2
14.36
15.
(~I-C&~RU
and (II-C~J&&~
Treatment of the ruthenium complexes (15.1, cyclopentadiene gave ruthenocene
Q 0
Ru
(PPh3)2X
IS.1
References ps128
[2.793.
X =
H, Cl) with
106 Ruthenocene
underwent
+0.68 v, 100 mv s
-1
, on voltammetry
AlCl3:n-butylpyridinium
chloride
electrodes.
In acidic
was
by a multistep
oxidized
composition The
have
melts
of the melt
corresponding
shifts
and compared
ferrocenophanes
The reduction borohydride
acid produced
Irradiation
on the nature
In addition
ruthenocenophanes
[3]ruthenocenophan-l-one
the values
with
chloride,
substitution
[202].
with
the product Carbon
of ruthenocene,
and dichloromethane
the formation
sodium borontrif'luoride
in ethanol-polychloromethane
ethoxycarbonylation
containing
for the
of the polychloromethane.
to substitution,
with
cyclopentenes
ruthenocene 3 sensitive to the
I,1 I-diethylruthenocene
depending
formylation
ratio carbon
of AlCl was
several
and
of aluminium
led to photochemical
oxidation
for
with
of ruthenocene
caused
which
Lp,2 =
[Zol].
solutions
chloride
vitreous
of l,l'-diacetylruthenocene
in the presence
or sulphuric
using
an excess
sequence
[k]ruthenocenophan-Z-one
been measured
caused
in an 0.8:1 molar
melt
with
oxidation,
[Zoo].
I3 C NKR chemical
including
an irreversible
carbon of
chloro
caused
tetra-
ChlOrOfOrm
ethoxymethglation.
tetrachloride
favoured
[(~-C5H5)2R~]tR~C14and trichloromethyl
and substituents
[283]. Perrocenylruthenocene coupling
in the melt.
Mass
lower metal-ligand
[?84].
Q-9 0
(15.2) has
of iodoruthenocene
0
with
spectrometry bond
strength
been
a large
obtained
excess
of the complex
by Ullmann
of iodoferrocene (I:>._')indicated
for iron than for ruthenium
107 The [3.3](1,1~)-
and (S,S](l,l')-ruthenocenophanes and the
fefrocenoruthenocenophane homologues have been prepared. For example, the reaction Of ?,I'-ruthenocenedicarboxaldehyde with l,l'-diacetylruthenocene in ethanol in the presence ethoxide gave the ruthenocenophane
(15.3)
of
in good yield
Vinylruthenocene has been homopolymerized and
sodium
[285].
solution
copolymerized with methylacrylate,
styrene and vinylpyrrolidine in the presence of azobisisobutyronitrile as catalyst. The
Pollers 3.13
x
were benzene soluble with molecular weights of 103-1 .3
3.1-13.2. analysis
x 705 and molecular weight distributions of
The polymers were investigated by thermogravimetric [286].
Polyruthenocenylene oligomers have been prepared by the coupling of the l,lf-dilithioruthenocene-1,2-bis(dimethylamino~ethane complex in the presence of copper
chloride [287].
Hydroxyfase activity in rats and mice has been studied using 103 Ru-ruthenocene. Greater hydroxylation was observed in male than in female animals and after pretreatment with barbiturates.
The distribution of 103 Ru in lung and kidney
after administration of 103 Ru-ruthenocene was affected by barbit;;ate pretreatment
[28S).
Ru-Labelled ruthenocenecarbaldehyde was treated with glucosamine, galaotosamine and mannosamine to give the oorresponding Schiff bases which were reduced at the C=N bond and the aldehyde
14C-Labelled glucosamine was also condensed
group.
with ruthenocenecarbaldehyde
to give the corresponding labelled
amino sugar derivative of ruthenocene
[289].
The metabolism of ruthenocene derivatives ofamino-sugars labelled with lo3Ru has been investigated. The derivatives were concentrated in the kidney and liver of tumour-bearing mice and excretion was rapid as the unmetabolized amino-sugar. stability
of
results
[290].
16.
The
the ruthenocene group was demonstrated by these
h-CpSNOh~CS~;~
Dicarbonyl(n,-cyclopentadienyl)cobalt combined with l,2(16.1) to form 1,2,4-triphenyl-3(~-~henylethynylphenyl)biphenylene as the major product together with the (y-cyclobutadiene)cobalt and (q-cyclopentadienone)cobalt
bis(phenylethynyl)benzene
Referencesp. 128
108
*
'Ph
I
16.1
‘Ph
16.2
complexes
(16.2 and 16.3)
(n,-cYclobutadierle)cobalt X-ray
crystallography,
respectively. complex
The related
(y-cyclopentadienyl)rhodium
and
The structure
(16.2) has reaction
the ligand
of the
been confirmed
by
of dicarbonyl(16.1) was reported
[291].
Coupling
;
constants,
J(C1-C?)
and J(C2-H)
the former trigonal
been
obtained
(v, -dlpnenylmethoxycyclobutadiene)-
C IJDiRsnectroscopy for by tricarbonylcobaltium hexafluorophosphate.
was
have
4 -. .
13
was
the lowest
carbon
atoms.
in accordance
with
reported
The value values
The value
for l-bond
for the latter
previously
the separation
of closely
related
for
between
was high
reported
c Y clobutadier.e)tricerbonyliron complexes '"\High performance liquid chromatography
obtained
coupling
and
for substituted
[292]. has been used
(T-cyclobutadiene)-
for
109
16.4
16.5
(I-cyclopentadienyl)cobalt complexes such as diastereoisomers and structural isomers. Reversed phase chromatography has been used with octadecylsilyl-modified silica as a stationary phase and
pOLa??
mobile phases saturated with argon.
Thus the diastereoisomers (16.4 and 16.5) which were inseparable by 4LC Were conveniently separated using acetonitrile/water (9/l) [293, 2941. Cyclic voltammetry and polarography have been used to show that (y-cyclobutadiene)(\-cyclopentadienyl)cobalt underwent reversible electrochemical oxidation [2953. The mechanism of formation of \4-cyclobutadiene-metal compounds, by the interaction of transition metal complexes with alkynes, has been investigated. and 16.8)
were
Compounds of the type (16.6
subject to flash vacuum pyrolysis and extensive
eouilibration between these two compounds was observed.
From
the results it was concluded that the cobalt complexes (16.6 and 16.8) reversibly isomerized through the intermediate (16.7) by single alkyne rotation [296]. Gas phase rearrangement of the (y-cyclobutadiene)cobalt complex (16.9; R1 = Rz = SiMe3, R 3= R4_- CECH) gave the product (16.9;
R1
=
R*
=
C=_CSiPiej,
R3 = R4 = H).
It was considered that
the corresponding rearrangement of the complex (16.9; R' = R2 = H, R3 = R4 = CECH) could involve the intermediate (16.10) [297]. The treatment of the t\-tetraphenyl-cobalt complex (16.11) with lithium tetrachloropalladate(I1) in the presence of sodium acetate gave the ortho-palladated compound (16.12).
The
reactions of this latter compound with carbon monoxide and
References
p. 128
110
H SiMe
SiMe co
3
3
3
16.7
16.6
%
16.8
R1
R4
16.9
16.10
111
Ph
Ph
Ph
Ph
Ph
Ph
NMe2 I Td-
Cl
2 16.11
16.12
olef'ins were examined
[298].
A complete product analysis for the reaction of dicarbonyl(y-cyclopentadienyl)cobalt with 1,6-bis(trimethylsilyl)-l,~hexadiyne has been carried out.
Eighteen metal complexes were characterized and these were formed by oligomerization of the diyne to give mixed cyclobutadienes, cyclopentadienones and
biscarbgne clusters [299]. (q4-Cyclooctadiene)- and (q4-cyclooctatetraene)(n\-cyclopentadienyl)cobalt have been investigated electrochemically.
For both the complexes the l,S-bonded isomer was
thermodynamically more stable in the neutral compounds and less stable in the anions on reduction [300]. 17.
Cobaltocene has been obtained in 52% yield by heating cyclopentadiene with cobalt(I1) ethoxide and diethylamine [301-j* In a similar preparation cobalt(I1) ethoxide was treated with cyclopentadiene in the presence of sodium cyclopentadienide [302]. Reaction of sodium cyclopentadienide with ethyl formate, methyl acetate or methylcarbonate afforded the substituted sodium cyclopentadienide derivatives (17.1; R = H, Me and OMe) respectively. Reaction of the organosodium reagents (17.1; R = Me, OMe) with cobalt(II) chloride or nickel(I1) bromide produced the corresponding cobaltocene and nickelocene
References
p. 128
112
Q
i Q
C=CH2
COR
0
COR
0
co
(CO$ COR
17.2
17.1
17.3
I
R
0
CHOCOCH=CH2
Q CO
17.4
(17.2;
derivatives
M
cyclopentadienide as precursors monomers
= Co,
Ni; R = Me, OMe).
derivatives
(17.1;
in the preparation
(17.3
17.i~)
and
The reaction
[303,
of the new organometallic
3041.
of dicarbonyl(l-cyclopentadienyl)cobalt
cyclohepta-1,3-diene
and cyclohepta-1,3,S-triene
corresponding
complexes
abstraction gave
cobalt from
the stable
(17.6) with
cation
(17.7).
(17.9).
and 17.6).
Proton
produced
gave
Hydride
abstraction
the anion
gave
Hydride
the
with the
of complex from
(17.8)
of dicarbonyl(l-cyclopentadienyl)cobalt
or 1,3-cyclohexadiene complex
(17.5
(17.5) or protonation
complex
n-butyllithium
Reaction
The sodium
R = H, Pie, OIGe) were used
[33;]. with
(q4-1,3-cyclohexadiene)-cobalt
abstraction
produced
(17.6)
complex
the dication
1,4-
\Q/ co
/\ / 0
6
6
17.5
17.6
113
co
0
0
:0,\. ,’
‘._-’
CO
_6 0
17.7
(17.10).
+
s1 o0
CO
6 0
17.8
Treatment of the dication (17.10) with sodium methoxide
or sodium cyclopentadienide gave double, vicinal and stereospecific (exo) addition to the benzene ring in accord with the Davies-Green-Bingos rules [306]. The photolysis of (r\-C5H5)Co(CO)2 in an aromatic solvent such as benzene or toluene afforded the corresponding (?-C5RS)Co(y-arene) and (r\-CSHS)Co(l-arene)2 complexes. The benzene complex (~-C5HS)C~(~-C6H6) combined with Z-butyne to give the hexamethylbenzene derivative (y-C5HS)Co(y-C6Me6) but failed to catalyse the formation of free hexamethylbenzene from an excess of 2-butyne [307]. Decamethylcobaltocene has been prepared from (MeOCH2CH20Me)CoBr2 and lithium pentamethylcyclopentadienyl and it readily underwent reaction with the electrophiles RX (MeI, Phi, ClCR2I, References
p. 128
114
(=j
p-
2+
co
co
6
t0
0
~
.
17.10
17.9
MeOCH2C1, MeCKClI) to give the products of oxidative addition (17.11).
This reaction with the chl.oroiodoalkanes gave the
corresponding exo-chloroalkyl derivatives (17.11) and these compounds underwent solvolytic ring expansion to form the n\-cyclohexadienyl cations (17.12; R = H, Me) [3081. The y4-cyclopentadiene compounds (17.13; X1 = Ph, pie;
R2 = Me) rearranged the corresponding Treatment
when heated cobalt
of these
or triphenylmethyl cobaltocenium
salts
in methylcyclohexane
complexes
complexes
with
to give
(17.13; R1 = H, R' = Ph, Me). ammonium
hexaf'luorophosphate
hexafluorophosphate
produced
(17.14; R = Ph, Ne)
the corresponding
[309].
Several reactions of' di(q-cyclopentadienyl)dicobalttetraiodide have been reported including reduction with sodium amalgam to form cobaltocene
c310 I+
0 *
+
0
.-: -3 *
CO
** -. .
co
R
l
'L
R
17.11
17.12
115
R
0 0 CO
0
t\
17.13
17.14
Thallium-cyclopentadienide
and -methylcyclopentadienide
treated with rhodium(II1) chloride to give the rhodocenium cations (17.15; R1 = R2 =H; R1 = H, R2 = Me; R1 = R2 = Me).
Were
Oxidation of the latter two complexes with potassium permangana te produced the corresponding acids which were converted to the acid chlorides (17.15; R1 = H, R2 = COCl; R1 = R2 = COCl). Treatment of the acid chlorides with sodium azide gave the amides (17.15; R' = H, R2 = CONH2; R' = R2 = CONH2) [311]. The reaction of tetraacetatodirhodium with pentakis(methoxycarbonyl)cyclopentadiene unexpectedly produced the rhodocenium salt (17.16) where two of the C02Me groups in each The structure of the salt (17.16) was determined by X-ray analysis. Both the CS-rings were ring had been replaced by H.
-bonded and they were fully staggered which allowed the bulky
Q b
1k
R'
C02Me
Me02C
0
Rh
0
Rh
R2
C02Me
Me02C
Co2Me 17.15 References
p. 128
17.16
116 C02Ne
groups
to intermesh
Addition
of the ?-diborabenzene
trifluoroacetic sandwich
electron
corresponding
complex
acid at -80 '6 nroduced
complex
valence
[312].
("7.18; n = 2) in high complex
singly
(17.17)
yield.
.Phis thirty
was electrochemically 31 electron
charged
to
the tri!jle-decided
reduced
cation
to the
(17.18; n = I)
[313]. n+
7% -Q0
0
Rh
Rh
Rh 17.17
0
17.18
+ The 'E and cobaltocenium preted.
C IPIR svectra
spectra It was
density
over
central
metal
(17.19)
yield
were
compared
concluded
the metallocene atom
Electrochemical
cation
of a series
hexafluorophosphates
The
analogues.
13
in acid (17.20)
that
of s-methyl-
have
been
recorded
with
those
of the ferrocene
the distribution
molecules
and inter-
of electron
was dominated
by the
[314-J. reduction
solution isolated
gave
of the cobaltocenium
cation
the hydroxymethylcobaltocenium
as the tetraphenylborate
salt in 602
[315]. Attack
lithium cobalt
gave
of the cobaltocenium the corresponding
complexes
(17.21; R = Me,
hydride
abstractinn
to give
the substituted
respectively
cation
[316].
with
with methyl-
exo-substituted Ph) which
triphenylmethylium cobaltocenium
or phenyl-
(v-cyclopentadiene)-
underwent
e-
tetrafluoroborate
cations
(17.~2; R = Pie, Ph)
117
Q
-I-
CH20H
Co2Et
0
CO
17.19
I
17.20
Cobaltocenium halides were prepared by oxidizing cobaltocene with 0.01-0.03 M bromine or iodine in a hydrocarbon-tetrahydrof'uran solvent mixture at O-5 ' in an inert atmosphere
[317].
R H +
Q
R
0
4
CO
6 0
6
17.21
0
17.22
The intercalation compound Zr(HP0 ) 4 l.5(po4)o.s [V5H5)2Colo.~ has been obtained by treatment of cobaltocene r*ith ZI?(HPO~)~.H~O [318]. Nesmeyanov and co-workers have reported a method for improving the strength and yield of l,l'-diacetylcobaltocenium hexafluorophosphate copolymers
[319]. Mercaptoorganosiloxanes were used, with cobaltocene as catalyst, to prepare one-package sealing compositions which were
stable in the absence of oxygen and were cured in the presence of oxygen [320].
References
p. 128
118 18.
Cobalt-carbon Cluster Compounds The cobalt-carbon cluster compounds
[i8.1; R = CH CO Ne, 2 2 CH(CO2Me)2] were formed unexpectedly by the reaction of methyl acetylenecarboxylate or di(methy1) acety lened icarboxylate with [321].
COAX
i
(co)3co-
c\/ /I
I\
coom3
co(co)3
18.1
Prolonged reaction of sodium tetracarbonylcobaltate with (ClMe2Si)2 gave the cobalt cluster compounds (18.2 and 16.3) [322].
The alkylidynecobalt nonacarbonyl complexes (18.4; X = Cl, Br, H) have been prepared in a one step process.
Cobalt(i1)
nitrate in aqueous ammonia was reduced with sodium dithionite under an atmosphere of carbon monoxide at room pressure in the presence of a benzene solution of the halocarbon containing cetyltrimethylammoniutn bromide as the phase transfer catalyst.
OSiMe2SiMe2Co(CO)
4
c\co(co, / \
SiMe2 \Co(CO)
3
(co)3co
/I -Co(COj3
18.2
(CO)3GO-
/I
3
WI82
18.3
119
i
c\CO(Co) / / 3 I/ \I \/l I
(CO) co3
w3c
Co(CO)3
\
,L
o----co(co)3
18.5
18.8
The cobalt cluster complex was isolated from the organic layer after two hours
[323].
An unsuccessful attempt has been made to prepare alkylidynetrirhodium complexes by the reaction of Na[Rh(C0)2(PPh3)2]with The major product was RhX(CO)(PPh,)., where halocarbons. ,'L X = Cl, Br [324]. The methyl substituted cluster complex C18.5; Y = Co(CO)3] has been treated with (l-cyclopentadienyl)metal carbonyls to _ give the derivatives
[18.5;
Y
=
Mo(~-C~H~)(CO)~, W(Y-C~H~)(CO)~,
Fe(y-C5H5)C0, Ni(T-CsHS)] [325]. Treatment of the cobalt complex (18.6)
with the hydrides
R3MH (M = Si, R3 = Me3, Ph3, Me2C1, MePhCl; M = Ge, R3 = Ph3, Et?, Ph2C1, Et2C1) produced the corresponding silicon and Alcoholysis of chlorosilane germanium derivatives (18.7). H
MR
I
c~coo / I\A
I3
3
(CO)po
-co(co)3
18.6
References p. 128
18.7
120 (18.7;
derivative alkoxy with
MR3
derivatives.
= SiYIePhCl) gave These
i-Bu,Al;I or Et,OBF
hydride
alkoxy
to give
the corresponding
compounds
underwent
the corresponainr:
reaction
siiicon
or fluorideLM[32z].
The silicon-
and germanium-cluster
complexes
(16.d; M = Si,
, Ph) have been formed by metal exchan:;e with a Ce, R = ;h?;e preformed cluster or by synthesis from cicobalt octacarbonyl and
[327 3.
(q,-C5H4)(CO) 3NoSiH$Ie
i
o0
I’\corco, / 3 /I \ Co(CO)_
No-
3
(coj2 18.8
The Crystal
and molecular
nonacarbonyltricobalt have
been
determined
cluster by X-ray
complex
(16.4; X = Cl) shows
mesityl
complex
imparting
of the methylidyne(18.4; X = Cl, C6H211e3) i'he cihloro
crystallography. the expected
structure
while
the
(18.4; X = C H Me ) snows interaction between 62 3 group of the substituent and the neighbouring
the g-methyl carbonyl
structure complexes
ligands
forcing
some bridging
Ultraviolet
the latter character
photoelectron
on the co balt
calculations
into
the Co -plane 3
and
[34.
spectra
complexes
and molecular
orbital
(lil.1; H = H, Me,
Oldie,Cl,
It was suggested that the apical Br, I) have been reported. carbon was electron rich and that the T-system was sufficiently flexible concluded
to behave
as either
that
the CR group
The He(I)
photoelectron
a donor
It was
or acceptor.
was best
described
as sp 'hybridized
[329]. complexes
(16.1~;
on the basis consistent
X
of qualitative
with
s!?ectra of the cobalt
= F, Cl, Pie) have
arguments.
the interpretation
cluster
been measured
and interpreted
The results
of the cluster
were
as an electron
121
i t
co(co~3
- 1 /
(co)3co
\/
co (CO1.pPh3
18.10
18.9
sink which underwent %in-l;eraction with the substituent X [330]. The radical anion cluster complex (lS.9; X = Ph, Cl) was
obtained by electrochemical reduction and underwent nucleophilic substitution with phosphines and phosphites to f'orxn products such as the triphenylphosphine (18.10) [331]. Treatment of the tricobalt clusters c18.11; R = CONMe2, Cl, R, Ph, Ne; L = CO, PMej, P(OMe)3J with ~e*A~N~e~ gave intermediate substitution products which were highly susceptible tQ hydrolysis and derivatives (18.12) of the bidentate Ligand (Ivie2As)20 were isolated, The same compounds (28.12; L = CO) were obtained by direct substitution of the cobalt clusters (la.l?; L = co) by (Me2As)20 together with the corresponding di- and tri-substituted products
18.11
References p.128
[332].
18.12
122
18.13
18.14
The cobalt cluster compound (18.13) underwent reaction with hydrogen in aromatic solvents to give 3,3-dimethylbutene, The hydrogenation 2,2_dimethylbutane and &,4-dimethylpentanal. was inhibited by the presence of carbon monoxide [333]. Acyl- and aroyl-methyl~dynetr~cobaltnonacarbonyl cluster complexes (18.14; R = H, Me, Et, Bun, 4-Br.C&+, 4-C1.CgH4, 4-FIe.C6H4, Ph) underwent reduction with hydrogen in 4-F+& ref'luxing benzene to give sither the N-hydroxyalkylidyne complexes (18.15) or the completely reduced alkylidyne complexes (q8.16) or in some cases
a mixture
of
the
two
products.
%hen
tne reagent was trifluoroacetic acid then the alkylidyne clusters (18.16) were the exclusive products. Thermal. decarbonylation of the complexes (18.14) gave the corresponding aikyl- and arYlmethylidyne cluster complexes (18.1; R = kt, Bun, Pr', 4-Br.Cbff47
CHOHR
CH2R
I
I
18.15
18.16
123
4-cl.cbH4, 4-F.C H4, 4-Me.C6H4, Ph, 4-Me2N.C6H4, ferrocenyl, 2-pyrrolyl) [334 4 . 19.
(1\-C&@i The nickelocenes
(19.1; R = H, Et) have been prepared by reaction of the corresponding lithium cyclopentadienide with nickel chloride. 1.65 THF
0
335 .
R
*
-6-b \ /
Ni
Ni
Ni
0
R
q 19.1
19.2
Treatment of nickel(I1) chloride with bis(l-cyclopentadienyl)magnesium gave nickelocene in '72% yield
[336].
The cluster complex (T-C5HS)3Ni3(C0)2 was degraded by
heating with triphenylphosphine in THF to give a mixture of nickelocene, (PPh3)3Ni(CO) and (PPh3)2Ni(C0)2. mechanism was discussed
The reaction
[337].
The disordered phase of nickelocene at 295 OK was investigated by an X-ray diffraction study and compared with that of ferrocene.
The results showed that the evolution of the
disordered phase of nickelocene and ferrocene between 295' and _!? OK was different
[338].
The structure of bis(v-fulvalene)dinickel determined by X-ray crystallography.
(19.2) has been
The C-C bond distances
were found to show localization of multiple C-C bonding as in the neutral ligand [339]. The collison
free molecular
multiphonon dissociation (MPD)
and molecular multiphonon ionization (MPI) of nickelocene induced by the light region
References
of a tunable
dye laser in the wavelength Four reactive
3750-5200 A has been investigated.
p. 128
124 Processes
were
identified,
3.10 ev, 3-photon 3;>>2.&
and j-photon
Nultip‘hoton been
studied
resonant
have
which
recorded
resulted
decker
showed
ions produced
at 30-300
OK.
from
discussed
conformational
complex
(19.3) have
over both
The electrochemistry
melts,
a reversible
of
ratio
one-electron
ion were
ir: acidic oxidation formation
19.3
found
melts, to
atoms
the
(3PC) melt
has been
reaction
dication
ion
underwith
an d the
in chloride
ratio
nickelocecium
studied.
nicXelocene
Both nrckelocene
to be unstable
of a stable
electron
[31+33.
at 40 'C in an aluminium
AlC13:BPC,
molar
and analysed.
and -Ghe unpaired
charge-trarlsfer
>I:1
disorder
13~2 3.
been recorded
nickel
chloride
.]:I molar
El = -(;.I65 V vs. Al reference.
reversible
compounds
of tile pars-magnetic triple-
of' nickelocene
chloride-1 -bvtylpy-idiziurr
spontaneous
and non-
of dynamic
fluctuations
and '3 C WKEI spectra
distributed
solvents.
beams.
exclusive
by resonant
in terms
be‘naved like a metalloceno
n?ckelocenium
molecular
almost
has
The temperature dependence -1 ) and q.uasi-elastic
The complex
went
[jlr(j].
perdeuterated
was equally
In neutral
eV
s;:ectra (lo-200 cm
'PI, "B
sandwich
>
(10-4~~0 cm -I) of nickelocene
spectra
and the corresponding
scatterln;5 were
The
and in supersonic
and infrared
the low frequency neutron
?.6-1.9
IbiPIfor%_,
;j-photon M~i) for
[3413.
mechanisms
been
=
eV,
of nicirelocene arid frrrocene
ion detection
of bare metal
and ferrocene
molecular
3.1G-2.10
for%2
MPD
in effusive
The Raman
=
dissociation
FIaSs snectrometric generation
two-photon
TOP&J
NPI
rich
AlCl,:Ui'C, xzsiobserved
with
at E-2 = +0.91- ’ v vs.
19.4
Al.
125 The electronic spectra of nickelocene s-;ecies in the +2, +3 and +4 oxidation states have been obtained in the melts [344]. Bickelocene has been used in the preparation of the phosphine complexes [19.4; L = PPh3, Ph(n-BuJ2P, PhMe2P, Ph2MeP, (n-Bu)3P, Et3P; L2 = diphos, o-phen, bipy].
The mechanism of
substitution of nickelocene was discussed [345]. Reaction of nickelocene with the bis-ylids Ph3PCH(CH2JnCHPPh 3 (n = I-3) gave the corresponding chelate complexes (19.5). Treatment of nickelocene with the mono-ylids ethylidenetriphenylphosphorane and triphenylphosphoniumcyclopentadienylid
afforded
the cations (19.6 and 19.7) respectively [346]. Reaction of nickelocene with HP(0)(OR)2, (R = Me, fit) produced the corresponding nickelbis(phosphonate)
Q
+
Q /*=\ 0
Ph3PCH
CHPPh3
\/
Q 0
Ni
PPh3
References
p. 128
/*=\ Ph3PHC
CHPPh3 I Me
Me
19.6
19.5
2+
1
+
0
I
(CH2)n
PPh3
COmpleXeS
(?-CgHg)~Ji~['(Ol~)20]2N)which contained a six-membered NiP02Ei ring with a symmetrical O-H-O hydrogen bond [3!~7]. The reaction of nickelocene with Ru,(GO)12 gave [(rj-C~H;)Ru(Co),],,r\-C5HsNiRu3(CO)9 and'with liRu(GOjqC~2Butthe hydride F~Ru~(CO)~C~E$~ [348-j. (?'-Alkerlyl)(n;?-cyclonentadienyl)nickelcomplexes were prepared from nickelocene by treatment with alkenylmagnesium halides, isopropylmagnesium bromide and alkadienes or with methylenecycloalkanes
[349].
X3-7-Fhosphanorbornenes
have been prepared by reduction of
the corresponding phosphorus sulphides with nickelocene in the presence of propyl iodide [350]. Slocum and co-workers have demonstrated the potential of T-bonded organometallic polymers in catalyst design.
'The
reaction of cobaltocene with the tetracyclone ligand produced (q-cyclopentadienyl)(l-tetracyclone)cobalt
and t'he same reaction
with nickelocene afforded bis(q-tetracyclone)nickel 20.
[311].
'~q-+jE&U Activated uranium prepared by the reduction of uranium(IV)
chloride with sodium-potassium alloy in dimethoxyethane, has been treated with cyclooctatetraene to form uranocene in 4090 yield
[352].
Uranocene has been prepared by treating uranium with cyclooctatetraene at room temper-.ture. The thermal behaviour of uranocene was investigated.
Between 575-680 'ii it sublimed
and above 680 ' decomposition occurred to give uranium and cgclooctatetraene
[3533.
Lithium hexaalkylu~anate(IV) complexes combined with cyclooctatetraene to form uranocene in good yield [3!&]. The substituted uranocene (20.1) has been prepared by the reaction of uranium(IV) chloride with the cyclobutenocyclooctatetraene dianion [3553. Bis (~-bicy~loo~tatetrae~yl)d~urani~, "biuranocenylene" (20.2) has been obtained, together with l,ll-bis(cyclooctatetraenyl)uranocene, by treatment of bicyclooctatetraenyl :\rith potassium in THF and then uranium(IV) chloride [356]. Uranocene has been reduced with lithium naphthalenide in tetrahydrofuran to give [~(c~~~)~]-L~,',THF. 1WR an,d ZSR data
127
U
d 0
20.2
20.1
indicated that this anion had a sandwich structure and that U(II1) was present [357]. The reaction of uranocene with iodine gave UC 16H.,21q which could be sublimed under reduced pressure.
The infrared spectrum
of the product indicated the presence of a C-I bond and possible use of this compound for the preparation of ultra pure uranium was discussed
[358].
Oxidative-addition takes place at uranium in the bis(r\pentamethylcyclopentadienyl)uranium
complex (20.3; X = THF) with alkyl halides, such as Bu%l, PhCH2C1 and Me CCH2Cl, to 3 1. The form the complexes (20.3; X = Cl, Bun, CH2Ph, CH CI'Jie stoicheiometrics of the reactions were examined The bis(y-cyclopentadienyl)uranium
3.59 ;i. j. complex (20.4) was an
effective hydrogenation and polymerization catalyst for alkenes [360].
7% Tk UMe2
UClX
*
+ 20.3
References p. 128
20.4
128 BtiFZiRE:ICES K. Jonas,
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(W2
(CO);!
9.7
9.6
9.8
9.9
c 0
Mn
(Cop
9.10
9.27
CH-
CH(t-3u)2
53 carbyne ligands CMe+, CSiMe3+, CPh+ and CNEt2' and the metalContaining fragments (T-CgH5)Mn(C0)2 and Cr(CO)S have been investigated by a nonparametrised molecular orbital method. Calculations were carried out on four carbyne complexes made from these fragments: (?-CgH5)Mnn(CO)2CMe+, (?-CL;H5)~(CO)2SiMe?', (?-C5H5)Mn(C0)2CPh+ and (CO$CrCNtit2+. It was concluded that the orientation of nucleophilic attack on these complexes seemed to be frontier controlled and that the gross positive charge of the substrate molecule enhanced its overall reactivity towards nucleophiles 10.
[I591.
(q-Trimethylenemethane)Fe(C0)3 Complexes Molecular orbital theory has been used in a theoretical
investigation of the energies of low lying electronic states in the 2-methylenecyclopentane-1,3-diyl
ligand (10.1) [16O].
Ph
Fe (CO)3
10.1
10.3
10.2
.->
Fe2(C019
Ph
Ph
20 Oc Ph
Ph (COJLc
10.4
References
p. 128
10.5;
Fe GOI
10.6
54
The stereochemistry of ring opening of 2_phenylmethylenecyclopropane
(10.2) to tricarbonyl(r\-phenyltrimethylenemethane)-
iron (10.3) has been elucidated by stereospecific deuteriurn labelling.
The reaction of 2,2-diphenylmethylenecyclopropane
(10.4) with nonacarbonyldiiron gave the tetracarbonyliron complex (10*5), identified by X-ray crystallography, which underwent ring opening to form the (l-trimethylenemethane)iron ccmplex (10.6). The stereochemistry of the reaction mechanism was snown to be consistent with frontier molecular orbital symmetry considerations _ _
11.
(Acyclii:-?j-diene)Fe(COf3Complexes IJV irradiation of pentacarbonyliron with a mixture of
1,3-dienes and silanes gave mixtures of isomeric hydrosilylation 3 products. The reaction proceeded by way of intermediate (r\ anti-b~teny~)tricarbony~~ron-tr~alky~si~ieon complexes which were accessible by photoinduced addition of R3SiH to (n\-butadiene)tricarbonyliron and which on heating gave similar mixtures of isomeric butenyLtrialkyLsi.licon derivatives [162]. Treatment of the cyclopropenic ester (11.1) with enneacarbonyldiiron led initially to the l-allylcarbonyl complexes (11.2 and 11.3). When these compounds were heated decarbonylation and hydrogen migration occurred to produce the tricarbonyliron complexes (11.4 and 11.5). From this and related work it was concluded that (y3:q'-alLyJ.carbonyL)tricarbonyliron complexes were converted easily into (tri~arbony~)(~4-d~en~)i~on compounds whenever the possibility of hydrogen migration existed 11633. Reaction of the dibromide (11.6) with Fe2(CO)o produced the (r\-3,k-dimethylene-l,S-cycloheptadiene) complex (11.7). Treatment of the latter complex (11.7) with n-butyllithium folloued by water, deuterium oxide OP bsnzaldehyde gave the tricarbonyliron complexes rl1.8; R = Ii, II, CH(OH)Ph] respectively Tricarbonyl(~-2-pyrone)iron
combined with two nucleophiles
in succession to form substituted (y-butadiene)tricarbonyliron Thus treatment with n-butyllithiunl and then methyl-
complexes.
lithium gave tricarbonyl[?-(ZE,&E)-2,4-decadien-6-one]iron. Several reactions of this type were reported and a mechanism was proposed
[165].
Fe
11.1
Fe (co)3
(co)3
11
11.5
.h
Q I
CH2Br
BrH2C
H2C
\
I Fe
CHz
NOI
11.6
References
p. 128
11.7
w3
11.8
56
Irradiation of 2,3-dimethyl-1,3-butadiene with (q-X2= CHCO$ie)Fe (CO) gave the 1\4-di.cne-iron complex (11. ‘1). 4 Reaction of the complex (11.9) with carbon monoxide at >,-30 ' produced a mixture of the tricarbonyliron complexes El
=
R,
(11.10;
R2 = COTMe; Ri = CO2Me, R2 = Hj [IG].
X ‘I’ 11.10
11.9
The (q3-vinylcarbene)iron complex (11.11) was attacked by diazo compounds, N2CHR, where R = H, C02Xt, Eh, to form the (r,-butadienejifon complexes (l?.l%; R = H, CO2&Zt, Ph). mechanism appeared to invol.ve insertion of the of
The
mcthyiene
group
the diazo reagent into the carbene carbon-iron bond [167]* The main product from the reaction of 2,3,5,6-tetrakis-
(methylene)-'j'-oxabicyclo[2.2.l]heptanewith Fe,(COjq was bis(t~ica~bo~iyl~ron~comp~ex (17.13).
The
complex was determined by X-ray analysis.
structure
of
the
this
I of 'The a&i.tio-i
OMe
11.11
11.12
11.13
12.14
trifluoroacetic acid to the complex (11,13) gave initially a 7j3-Ed.lYl Complex then the trans-bis(~3-allyl)isomer high regioselectivity [168].
(11.14) with
T'b electronic structure of the complexes (T-diene)2Fe(CO), where diene = butadiene, dimethylbutadiene and 1,3-cyclohexadiene, has been investigated by He(I) photoelectron spectroscopy. The first seven bands in each spectrum were assigned using INDO calculations based on the ASCF procedure and the transition operator model. Bonding in the ground state of the parent complex (~-butad~ene)~Fe(~O), was discussed5p 691. The natural isotope abundance
Fe N!miRspectra of thirty-five
organoiron complexes, principally cyclic and acyclic (r\-diene)Fe(COj3, have been measured at 2.9 MRz by direct detection. The 57 Fe chemical shift range observed was 3000 ppm and most rBsonantes were at higher frequency than that of pentacarbonyliron which was used as a secondary standard. The 57 Fe shielding was discussed qualitatively in terms of charge distribution in the complexes with very large deshielding effects being observed for cationic olefinic ligands. The shielding in (I-dienejiron complexes was dependent upon ligand geometry and decreased with an Increase in C-C-C bond angle or with an increase in ligand ring size [170]. Moessbauer spectroscopy was used to study the dynamic ProPerties of (r\-butadiens)tricarbonyli.ronfilms on exfoliated graphite (1711. The infrared and Raman spectra of (T-butadienel- and (Y-hexadeuterobutadiene)-tricarbonylirOn have been recorded and
References
P. 128
58 interpreted
[I72-J.
Tricarbonyliron has been used as a protecting group for ‘I,?-dienes in the stereospecific synthesis of insect pheromones. Thus (~-butadiene)tr~carbonyliron was treated with Cl~O~C~~)~C~~~t and AlCl
under Friedel-Crafts conditions to form the (q-diene)-
iron comzlex (11.15) which was converted to the acetate (11.16) in two steps.
Decomplexation with trimethylamine N-oxide gave
the free pheromone, fX)-9,?1-dodecadienyl acetate, of the red Several. related pheromones were obtained in the
bollworm moth. same way
[173].
Fe
w3
11.16
11.15
Cationic polymerization of the (q-butadienejiron complex (11.17) with boron trifluoride etherate gave a methanol insoLuble
/----cf /\
polymer while the monomer (11.18) obtained by thermal
Fe (CO)3
I
F;e
(CO13
59
isomerization of the complex (11.17) was inert to cationic polymerization,
Polymers derived from related (r\-pentadiene)-
iron and -ruthenium complexes were chemically modified to contain the l-ally1 group and metal-metal bonds.
1,2-Polybutadiene and
3,4-polyisoprene combined with pentacarbonyliron and dodecacarbonyltriiron to yield polymers with (q-diene)iron groups in the main chain [174]. The (t\-butadiene)-iron and -ruthenium complexes (11.19; M = Fe, Ru) have been prepared as monomers and were polymerized with cationic initiators to give high molecular weight polymers (11.20; M = Fe, Ru).
These polymers were then protonated using
dry hydrogen chloride to form (y-allyl)metaltricarbonyl groups [I75 1. The tricarbonyliron derivative (11.21) has been resolved and used to prepare the optically active complexes (11.22 and 11.23). These complexes were used to prepare chiral electrophilic cyclopropanes [176]. The carboxaldehyde complex (11.24) has been treated with hydroxylamines to form the nitrones (11.25; R = Me, Ph) which underwent 1,3-cycloaddition with olefins to form the corresponding isoxazolidine complexes
[177]. The electronic effects in the tricarbonyl(y4-diene)iron
derivative (11.26) have been evaluated by pKa measurements on this compound and on the uncomplexed diene ligand. The results
M
(W3
11.19
References
p. 128
11.20
(C02Ple)2
Me0
2
C*CHO
/
lle02C \
Fe
bm3
/
-+ Fe
(CO),
11 .22
11 . 71
Me02C*
Fe
J2
(C02Me
m3
11.23
indicated it
that
reduced
the Fe(C0)
3
group
the electron-withdrawing
by disruption
of the conjugation
aromatic
[178].
Me0
2
ring
c~CHO
was electron
releasing
properties of' the dienyl
of the diene
system
c;roup with the
Me02C
Fe
(COj3
11.24
and that
11.25
61
11.26
mneacarbonyldiiron attacked the pcntaene 5,6,7,8_tetrakis_ (methylene)bicyclo~2.2,2]o~t-2 -ene in hexane-methanol to form the endo,exo-bis(tricarbonyliron) complex (11.27) and the structure of this complex has been determined by X-ray crystallography . The asymmetric arrangement of the two Fe(CO)3 groups was used to induce either stereospecific functionalization of the uncoordinated endocyclic olefinic bond or stereo- and regioSpeCifiC functionalization of one of the two coordinated s-cisbutadiene groups of the complex. Thus hydroboration/oxidation
of the Complex (11.27) gave the _endo,exo-bisftricarbonyliron)bicyclooctane-2-01 (11.28) while cis-deuteration was achieved with D /I%0
in hexane to form the _, endo
exe-complex
(11.29).
Proton~tion'of' the initial complex (12.27) with HCI/Al.Cl /CH2C12 gave the *\3-dienyl cation (11.30) which was quenched wit2 /CH OH to form the tetraene complex (11.31) by 1,4-addition S:ereospecific acetylation of the same complex (11.27) with CH3COC1/AlC13 in dichloromethane afforded exclusively the endo-derivative
(?1.32) which isomerized in solution to the
thermodynamically preferred form
(11.33).
The crystal and
molecular structure of the complex (11.321 was confirmed by X-ray Several related reactions were reported [ISO]. crystallography. The acetol.yses of the brosylates (11.34, 11.35 and 11.36) The acetolysis of the have been studied by 1H I%%? SpeCtrOSCOPy. complex (11.31;)was too slow to detect and that of the complexes (11,3& and 11.36) occurred with retention of configurations From the results it was concluded that homoconjugative stabilization n\-diene-Fe(C0)3 group can of a carbocation by an eXOCYcliC compete with its destabilizing inductive effect [loI]* References
p 128
62
3
11.29
L
Fe (CO) 3
Fe (CO)
Fe (CO13
Ge
m3
wN3 11.32
11.33
63
11.34
11.35
11.36
Reaction of the tricarbonyliron complex (11.37) with Me2As.M [M = Mn(CO)4PMe3, Fe(CO)2(?-C H ), Mo(C0)3(~j-CgH~), Mo(C0)2(r\-C5HS)PMe3, W(CO)3(?-C5HS), 5W?CO)2(?j-C5H5)PNe3 Jgave, for example, the tetracarbonyliron complexes [11.38; M = Mn(C0)3PMe , Mo(7\-C5H 5 )(CO),], (11.39) and (q-C5HS)(C0)3WAsMe2Fe(C0)3?sMe2L [L = Fe(C0)2(r\-CSHS), Mo(CO)2(r\-CSH5)PMe3] [182]. The (r\-butadiene)iron and (y-heterobutadiene)iron complexes (11.40; X = CH, N; L = CO, PPh3, AsPh3, SbPh3) combined with 1,2-bis(diphenylphosphino)ethane (diphos) to form the derivatives Fe(C0) (diphos)diphos. A kinetic study of the reaction suggested 12 an (T\-butadiene)iron intermediate [183]. Friedel-Crafts acylation of the hexacarbonyldiiron complex (11.41) with acetyl chloride or benzyl chloride produced the corresponding tricarbonyliron complexes (Il.@; References
p. 128
R = Me, Ph) [I&].
64
)-VI
O’I’ 0 Fe
(m3
,\/
Fe
(CO)
1"
.37
4
Il.36
0
II.39
11
.i+o
0
/\ 4Fe
11.41
ll.iL2
R
65 12.
(7\-C,+q)Fe(C0)3 Cocondensation of arenes with iron atoms at -196
the complexes Fexlarene)
'C
gave
which combined with hydrogen to form
-cyzl.onexadiene)iron complexes (IS.1;R=H, the mixed (r\-arene)(y Me, CMe3, Me3).
Vihencyclopentadiene replaced hydrogen as the
reagent then the (y-cyclohexadienyl)iron compl.exes (12.2; R = h, Me, CMe3, Me21 were formed
12.1
[185].
12.2
The reaction of 1,2-di-t-butyl-3,4,5,6-tetramethylbenxocyclobutadiene with nonacarbonyldiiron produced the two tricarbonyliron complexes (12.3
and 12.4).
The structures of these
complexes were confirmed by X-ray analysis 11106,1871. The crystal and molecular structure of tricarbonyl(y-1,2di-t-butyl-3,4,5,6-tetramethyLbenzocyclobu~adiene)iron
has been
Ph
Ph
"2.3
References
p. 128
12.4.
66 determined
by X-ray
analysis.
coordinated
in
the
was not
complex
because
the
some
of
ring
its
Atom
due
to
the
as a pure
cyclobutadiene
away from
the
to
the
tendency
energy
OT the
theory
electron
has
The
been
in
both
interpreted
of
monoxide
dienone
to
the
ring
to
retain
(&&D)
determine
tbat
was
in
a structure
close
agreement
[189].
of
solid
(r,-cyclobutadiene)tetracarbonyl-
and liquid
phases
matrix
at
12 OK gave
have
been
recorded
isolated
tricarbonyl
[I91 J. (q,-tetraphenylcyclobutadiene)iron underwent
P(0Me)3] a platinum electrode
pending
paramagnetic
same cations
complexes
methane
in
a
(r,-cyclopenta-
with
(12.5)
and were
intermediates
corresponding
Ph
in
(12.6)
AgBF4
and
neutral
by
oxidation
form
the
L = PPh3, oxidation
+ 1
the
formation
of
corresP(O?4e)j].
of
[N(4-Br.0684)4]PF’6 as
in
the dichloro-
tetrafluoroborate
The cations
salts. the
to
C12.6;
generated
were
(12.6)
the
cation
were
or implicated
(22.7)
from
(n,-tetraphenylcyclobutadiene)iron
Ph
Ph
Ph
Ph
Fe
cations
rl2.i’;
one-electron
dichloromethane
characterized in
complexes
reversible
radical.
hexafluorophosphate as
of
benzene
(y-butadiene)tricarbonyliron
L = PPh 3,
The
compl.ex
middle
) iron
The at
but
[I 901.
Photolysis carbon
the
ring
delocalization
used
results
IR and Raman spectra
molybdenum and
diffraction
was
[I&? J.
and el.ectron
tricarbonyl(r\-cyclobutadiene)iron
with
cyclobutadiene
shifted
resonance orbital
mode
group
regarded
was
superposition
molecular of
a tetrahapto
iron
b-membered
The tricarbonyliron
Ph
Ph Fe
(CO)*L
(W2L
12.5
12.6
tne
comple Ph
Ph
Ph Fe
12.7
X
+
67 and Silver nitrate and in similar oxidations.
Several related reactions of iron and ruthenium complexes were reported b92). Irradiation of monosubstituted tricarbonyl_(n,-cyclobutadiene)iron complexes in the presence of propgne gave isomeric mixtures of substituted toluenes.
The presence of electron-withdrawing
groups on the metal complex produced mixtures rich in the ortho isomer while electron-releasing groups favoured the para isomer [193]. (~-~enzo~yclobutadiene)d~carbonyln~trosy~~ron hexafluorophosphate was prepared by the reaction of (n,-benzocyclobutadiene)tricarbonyliron with nitronium or nitrosonlum salts.
The former
complex underwent facile reaction with RjM (M = P, As; R = Me, Ph) afford the +,-benzocyclobutenyliron complexes f(RjMc8R6)~e(CO)(~~O~~R3~+PF~- by a two step process involving nucleophilic to
addition and carbonyl substitution, In the same thesis the mass spectra of the manganese complexes (12.8; L1 = CO, L2 = Ph3P, Ph?As, Ph7sb; k1 = es, L2 = Ph,P, Ph.As, Ph,Sb) were also
CR'R'
12.8
12.9
A Hammett-Deno indicator acidity study using trifluoroacetic acid-water solutions was used. to determine PI&+ values for a series of tricarbonyl(f\-cyclobutadiene)iron carboeations (12.9; R1 = H, Ph, Me, R2 = Ph, ~-i'4eC6H4, Me). These carbocations were less stable than the corresponding ferrocene systems but more stable than a variety of similar organic and organometallic carbocations
Referencesp. 128
[19s],
I?.
(Cyclic-~-diene)Pe(C0)3
Complexes
(i) Formation ii%flCtiOE
with
Of
acetylenes
the
ITe2(CO)g gave
PhC%CWPh3
the complexes
(1~~ = $i, se, Sn, Pb)
i\ic-Lyle,.
(triphenylsilyl)-j,4-diphenyl-;
where
L = ,i,i;-bis-
,~,~-diphenyi-j,4-bis(iriphenyl-
zermyl.)-; :~,4-b-is(t:riphenjrlsta!-!nyl)-j,;-diphenyl-and ciiphenglbis(triphenylLplur?byl) -cgclo?encadierlone groups
Wefe
removed
the corresponding complexes
by treatment
The i-'hjPl acid
to give
tricarbonyl(~-dlphenylc~~rclo~ ontadienone)i.ron
[I%].
The \-gerlmacyclopentadiene-iron ~-PleG5H4, E-Fe2i.C6FIq, C6F5) have corresponding ment
respectively.
with hydrochloric
Eermacgclocentadiene
of t!le trisarbonyliron
(13.1,
complexes
been prepared
ti =
bt,
by reaction
with pentacarbonyliron.
complexes
.Pn,
030 the Treat-
(13.1, R = Pie, CZ;Ph,
gave the corres?onap-WeCbHjC, 2 -Me,MC 3 ) with tin tetrachloride 2 64 i)ecomplexatiorl of the ing exo- chl.oro derivatives (I3.2.). ligands
r\-germacyclopentadiene
Furt’ner
reactions
complexes
cI
was effected
:!:i;hke3!!0 and 'r'icl
4’
of the tricarbonylf7\-~ermacyclopentauienej
iron
[I971.
inieredescribed
c.I
\\ GB
,kcl
’
’
R
Fe
‘K
Fe
("O)3
UXN3
13.2
13.1
I,.!&-Cyclohexadienes with gemwith pcntacarbonyliron diene)iron
complexes Alkyl
the reactions. while
the C02,Me group
complex
with
comalexes oroducts
to form in order groups
(9 3.3;
to elucidate exertea
directed
the entering
substituents
attack
classical
of the correspondicg
effects
steric
by forming
tricarbongLiron
-created
(2,3-cycloinexa-
directing
group.
R = Me, Ph, CH2Ph) weTe formed
by treatment
‘nave been
the corresponding
in
r;indrance
an ir.cermezliate Thus
the
as the exclusive
1,4-cgclohexadienes
69
Fe
Fe
um3
(CO):,
13.3
13.4
with pentacarbonyliron while the products (13.4; Rl = C02Me, R2 = CH2C02Me; R ’ = Me, R2 = Ph) were each obtained as mixtures of two stereoisomers [Z983. The 3a-azoniaazulene complexes c13.5; R = ii, CHO, CH=CHCOCH3, X = 0; R = H, X = CHCIJ and 13.61 were prepared in
CH=C(COCH+,,
high yield by treatment of the free ligands with enneacarbonyI_-
13.6
13.5
I Fe
H
13.7
References
p. 128
70 diiron.
The tricarbonyliron
(13.7) was prepared
complex
also
[199]. Treatment
of s-
nonacarbonyldiiron complexes. produced 13.9)
Reaction the anti-
they both
triene)iron
the corresponding
of these
complexes
k&en the complexes
rearranged
to give
(13.8 and
(13.8 and 13.9) were
tricarbonyl(r\4-
cyclohepta-
Fe
(CO)
wN3
3
13.8
13.9
Thermal produced
reaction
of l,s-cyclooctadiene
in an ampoule
Reaction
was heated
and the tricarbonyliron
a mixture
of products of I-phenyl-
the phosphole-iron
produced
with
with nonacarbonyldiiron
complex
(13.10) was isolated
[202]. or I-t-butyl-3,4-dimethylphosphole
complexes
the corresponding
(CO)9
Fe
[201 .
tricarbonyl(l-l,S-cyclooctadiene)iron
1,5,9-Cyclododecatriene
with
nonacarbonyldiiron complexes
[200].
Fe
from
with
tetracarbonyliron
with
and s-norcaradieneiron
respectively.
heated
or &-tricyclo[3.2.O.O]hept-6-ene
produced
dimers
(13.11 and 13.12) respectively (13.13; R1 = R2 = Ph; R1 = R2 =
The structure of the complex t-Bu; R' = Ph, R2 = t-Bu). = R2 = The two Ph) was determined by X-ray analysis. RI phosphole strongly
rings
adopted
folded
a head
to tail
Bis(~5-heptamethylindenyl)iron
selective I-ene
cyclopentylation
of the complex similar
and iron(I1)
with
by dehydration to form
syntheses
were
has been
chloride
(n,-cyclohexadienyl)iron
followed
and they Were
[203].
heptamethylindene The
disposition
(13.13;
cation
prepared
(13.14)
underwent
regio-
l,Z-bis(trimethylsiloxy)cyclopent-
and dehydrogenation
the 2-arylcyclopentenone reported
from
[204].
(2051.
with
breakdown
(13.15).
Several
71
Fe
13.13
13.12
The rates
of
reaction
of
pentane-2,4-dione with a range of
t~~ca~bo~~~(~~ -cyclohexad~enyi)~ron cations (‘13.16;R = H, He, OMe) and for example (13.17; R' = Me, R2 = R3 = H; R1 = R3 =H, R2 = Me*f R' = R3 = H, R2 = OMe; R' = CO Me, R2 = R3 = H) have 2 been obtained under pseudo-first-order conditions. The rates
13.14
13.15
ii1
R2
7s-.
\
R
.__'
Fe
Fe
(CO)3
Km3
13.17
13.16
were
affected
position.
by the nature
For example,
and a 3-methoxy The enolate
group
of the substituent
a 2-methoxy
a slight
(q-cyclohexadienyl)lron anions Me
at the methylated
group
acceleration cation
caused
(13.18)
,- ‘._s
Me0 q Fe
Mm3 Fe (CO)3
13.19
Fe (CO)3
13.20
combineu
dienyliun: terminus
!
OH
retardation
[2~6].
1'
13.18
and by the
with
in a highly
73 regioselective reaction which was of importance in steroid and terpene synthesis.
Thus the enolate anion methyl 2-oxocyclo-
hexanecarboxylate gave the product (13.19) in 97% yield.
The
complex (13.20) was obtained in the same way and X-ray crystallography was used to determine the crystal and molecular
:,: ?I structure [207].
Reduction of the tricarbonyliron cation (13.21) to the
cyclohexadiene complexes (13.22 and 13.23) by a series of metal
1
‘.d’
Me
Fe
Fe
W3
Fe
(CO)j
13.21
NO)j
13.22
13.23
hydrides became less regioselective at lower temperatures.
In
contrast reduction by 9-borobicyclononane became more regioselective as the temperature was lowered [208]. The absolute configuration of the salt (13.24) has been defined and it has been used for the asymmetric synthesis of the x-disubstituted cyclohexenone (13.25) [209]. Alkylation of the (r\-cyclohexadienyl)iron cations (13.26; R1 = H, Me, OMe) with alkyllithiums, R2Li, where R2 = We, Pr',
+ I =v Me
PF6-
0
\
‘\
r
co2Et
bo2Et
13.24
References p. 128
13.25
74
Fe
Fe
(CO)3
(COJ3
13.27
13.20
13.26
Bun,
But,
in chloroform
at -78 'C gave
(y-cyclohexadiene)iron Pr', Bun,
But).
R1 = OHe)
gave with
(13.28;
(13.27;
products
In addition FriLi,
R = Pri, Bun,
was not observed
Fe
W3
But)
attacked
R1 = H, He, OMe; R2 = he,
to this product,
BunLi
and ButLi,
and the expected
by carbon
nucleophiles
gave a mixture
13.3:
rather
than the expected
and 13.32)
also underwent
The cation
(13.33) has been
of isomers
with
a variety
of the complex
tricarbonyliron
group
cyclohex-2-enone
of nitro-
a S-exo-nitromethyl
treated
NaCH(CO2l4e)2
have
been used The
R = OAc,
carbon
removal
of the
5-substituted
to provide
a route
atom corresponding phthalimido)
were
to give the (r\-cyclohexadiene)iron
Decomplexation
and treatment
the derivative
of the
a mixture
(ni-cyclohexadienylium)-
03S.C6114.Ne-4,
R = OAc, 03S.C6R4."'e-4,
nroducts.
R = phthalimido)
and subsequent
alkaloids.
(13.36;
(13.37;
Treatment gave
the corresponding
the quaternary
iron cations with
to be synthetically
cation.
[%I%].
complexes
containing
in Aspidosperma
acid gave
(13.30,
tricarbonyl-S-exo-
of nucleophiles
(13.34)
produced
(13.35)
Tricarbonyliron to compounds
princinal
shown
to the S-cyclohex-2-enone
(t3.33)
complexes
products.
The anion
to form
(13.29)
[Zll].
equivalent
to C-20
addition
addition
of the xetones
(2-oxobut-3-enyl)cyclohexa-l,?_dieneiron.
cation
regioselectivity
to give
ketone
derivative
(1j.26; products
tetrafluoroborate
Thus methylvinyl
methane
the cation
the isomeric
[210].
Tricarbonyl(q-cyclohexadienyl)iron was
the corresponding
with
(13.38)
phthalimido)
of the product aqueous
[213].
as the
(13.37;
methanolic
oxalic
\ \ / r G+ oi3t
BF -
4
0
O
+
\ /
Fe
Fe
um3
(cW3
13.31
13.30
13.29
0 OEt
+
\/ P Fe (CO
)3
13.32
0
Fe(C013
b
I’ --. R
cl I
R
Fs(CO),
13.33
13.34
13.35
The cations [($-dienyl)Fe(C0)3]+, where dienyl = C6H7, C6H60Me-2 and C7H9, combined with E-toluidine in acetonitrile to form adducts such as the (T-cyclohexadiene)iron complex (13.39). A
kinetic study of the reaction suggested that a two-step
References p. 128
Fe (Co+
T3.36
13.37
NH
Fk (co+ I 3.38 mechanism
was
E-toluidine
13.39
operating
with
to the dienyl
initial
reversible
ring followed
addition
by rapid
loss
of
of a proton
[214]. Tricarbonyl(q-cyclohexadienyliu.m)iron attacked
by anions,
JO-, to give
complexes
(13.40; R = H, Me,
binuclenr
products.
group
R and the reaction The cation
1,2,4-trimethoxycorresponding benzene were
Yields
gave
were
the tricarbonyliron for
in aduition
these
reactions
to
by the nature
of the
[215].
treated
with
1,3,5-,
1,3- and 1,4-dimethoxy-benzene
r\-diene complexes,
obtainec!
determined
conditions
was
cc\-cyclohexadiene)iron
But, Ph, SiMe3)
(13.42) has been and
the
tetrafluoroborate
For example, derivative and were
I,,?,?-, to give
the
1,2,4-trimethoxy-
(I3.41). interpreted
Rate
data
in terms
\iz;
OMe
OR
I
Fe
(COf3
73.40
13.41
of an electrophilic substitution mechanism that involved rapid preequilibrium formafian of aTT-complex followed by rate dstsrRapid proton mining rearrangement to a tieland-Gype s-complex. loss than gave the products [216], The nucleophilic attack of substituted pyridines on the tricarbonyl$-cyclohexadienyl)iron subject of a kinetic investigation.
cation (13.42) has been the The products were pgridinium
adducts (13.43; R = H, 2-Me, 3-Me, &-Me, 2,5-Ne2, 2,6-Me2, The rate of the second 3*54e2, 2,4,&-Me3, 4-Ph, Z-CR, 3-m). order reactions showed a marked dependence on pyridine basicitg. However, blocking of the 2- and 6-positlons of the pyridine by methyl. groups caused steric retardation. The corresponding
reactions
of tine cations
The tropylium tetraene)iron
[(~~-2MeOC&H6)Fe(C0)3]f
were
[(~5-C7R9)3'e(CO)3]+
ion
compared
attacked tricarbonyl(n,-cycloocta@+I+ the neutral complex (13.44) which contained
to form
a y-styrylcycloheptatriene indicated
that
was derived group
molecular X-ray
ligand.
Mechanistic
the cycloheptatriene
from
was formed
the tropylium
ring while
ion.
(13.44)
ti?e phenyl
The crystal
and
(13.4.4) was confirmed
of the complex
crystallography
proposals
ring in the complex
the cyclooctatetraene from
structure
and
[217].
by
[218].
Fe
w3
Reaction
of the close-carbaborane
2,3-Me2-2,j-C2BgHq
(r\-I$-cyclooctadiene)(?_cyclopentadienyl)iron toluene, ether
o-xylene
produced
complex. by X-ray 13.
The
or with
the corresponding6(q6structure
(ii) Spectroscopic The crystal
determined
by X-ray
these
PPh3] have
3' depopulation
L decreased orbital. model
rather
complexes
been recorded
was established
LUMO
Studies
of the
(y-cyclohexa-
L = CO) have been
The I3 C NIW spectra
of
[I3.45; X = H, OMe, L = P(OMe) 3' and interpreted in terms of as the T-acceptor
than the expected
An explanation
[220],
structures X = H, OMe,
crystallography.
of the diene
complex
and Physico-chemical
(13.45;
and the related
in petroleum-
arene)-close-carbaferraborane
[219].
and molecular
complexes
in benzene,
of naphthalene
of the 7\ -toluene
crystallography
diene)iron
AsPh
an excess
with
has been
enhanced
proposed
strength
population
using
of of the
a pictorial
KO
79
\e/ X
Fe
(CO)2L
-;2c-$JMe M;;p OMe Fe
Fe
NW3
(CO+
13.45
The crystal and molecular structure of bis[tricarbonyl(y-cyclopentadienone)iron]hydroquinone has been determined by X-ray methods.
The mo1ecul.e contains two tricarbonyl((-
cyclopentadienone)iron groups linked to hydroquinone by hydrogen bonds [221]. The structure of (~5-1-methyl-4-isopropylcyclohexadienyl)tricarbonyliron hexaf'luorophosphate has been determined by The cyclohexadienyl ring had a sofa conformation
X-ray analysis. [2223.
The thermal rearrangement of the (T-2-pyrone)iron complex (13.46)
to the isomer (13.47) has been investigated.
The crystal
and molecular structures of both complexes (13.46 and 13.47) have been determined by X-ray crystallography and a mechanism involving 3 -vinylcarbene)iron intermediate and a novel I,&-oxygen a (IJ
shift has been proposed [223]. The crystal and molecular structures of the (r,-cyclodeca-
Fe
(cm3 13.48
iteferences
p. 128
80 tetreene)iron
compl.ex (13.48) has beon
cr:Jstallo:~Taphy.
The tricerbonyliron
determined group
by X-ray
:;as bonded
to the
cis-3,5-diene rxG.t or” the ligand [2?bL). g_&..g, The XS,? s net tra of (1-7 , j-eye looctate traene ) iyGi3iij) ( -1,3-~~~~100c~~atetraene~-~'e(c0)3-
? recorded Tesided
and -Fe(Cti),,;‘Phj nave been
It was concluded
?nd interpreted.
in the cyclooctatetraene (n,-‘l,s-
:GLi spectra
for
showed
the unpaired
that
The application
Co-,
portion
t1;s.tthe oi:d electron
and 3, 3-cgclooctadicnej electron
of Frontier
(fi,-CLzii5)Co_.~
was predominantig
Orbital
?he
of r;he molecule.
theory
metal
centred
to cycloaddition
reactions of some tricarbonyliron complexes ‘has been investigated. 1 H iE;i spectroscopy showed that the reaction of totsacyanoethylene
with
13.49
the azepine
complex
(l.?.!.g4) gave
13.50
Fe
Fe
(co)3
13.51
-I 3.52
initiaily
the
81
1,3-addition product (13.50) which isomerized i;o the l,t3addition product (13.51). The initial formation of the I,?addition product Was in agreement with Frontier Orbital theory [226]. A kinetic study has been made of the addition of tetrato (y-cycl_oheptatriene)iron complexes (13.52; RI = H, CCMe, CHO, R2 = R, R1 = H, R2 = COMe) and to tricarbonyl(n,-cycIoheptatrienone)iron in several solvents. The tricarbonylcyanoethylene
iron group activated the complex and the reaction mechanism involved neither ionic nor free radical intermediates.
In one case (13.52; R1 = cH0, R2 = H) two parallel reactions were in competition [227]. The thermal isomerization of tricarbonyl(~-cyclohexadiene$-exo-h-d )iron (13.53) at 134 'C has been studied in order to --7
elucidate the mechanism of 1,5-hydrogen s‘hifts. Identical initial rates of 1E incorporation into the I- and 2-positions of the cyclohexadiene ring were observed.
These findings are
consistent only with a mechanism involving two sequential l,j-shifts of deuterium endo to the metal [228]. Oxidative cyclization of the (T-cyclohexadiene)iron complex (13.54) with anhydrous iron(II1) chloride on silica gel gave the tricarbonyliron complex (13.55) containing a tricyclic ligand. This reaction was in contrast to the behaviour of alcohols and (T-dienefiron complexes towards iron(II1) chloride [229].
OH
H
d7
d \/
I t
Fe (CO)3
13.53
References
p. 128
Fe (CO):,
82 The
(v-cyclohexadiene)iron
-H ) underwent
R"=p
concentrated
sulphuric
iron cation
(13.57;
Ii1 = H, R2 =V,-H) was
discussed
complex
acid catalyzed acid
to form the
R = II, Me).
(13.56;
Rl = H, CO$Ie,
decarbonylation
with
(r,-cyclohexadienylium)(? 3.56;
Iiowever, the complex
was unaffected.
The mechanism
of the reaction
[230].
_
r
+
R ,.--a : '._-
'P E'e
Fe
(COj3
wN3
13.5;6
13.s7
13.
(iii) General Birch
Chemistry
and co-workers
superimposed
lateral
have
control
structures,
by attachment
to olefinic
systems.
discussed
of reactivity,
of transition
The reactions
(T-cyclohexa-1,3-diene)iron
derivatives defined
substituted discussed
were
aryl cations in some detail
Elimination from
the diene
were
treated
corresponding Reaction
of both complexes
with
P(OPh)3]
were
and the trimethylsilyl
(13.58 and 13.59)
occurred
tetrafluoroborate
complexes
Related
and some cyclohexadiene
an ethylenebenzenium
cations,
when
to give
(13.60 and 13.61)
eta-7,9-diene
with
group
they the
(Z-321.
(benzylidene-
or Fe2(CO)
L = CO).
tetrafluoroboric
the derived of specifically
[231].
triphenylmethyl
The tricarbonyliron with
and
derivatives
tricarbonyl-
especially
as equivalents
the hydride
of dispiro[2.0.2.4]d
(13.62;
stereochemistry
or as cyclohex-2-enone
tricarbonyliron
acetone)tricarbonyliron complex
of
metal. carbonyl
of substituted
dienyliron
salts which
the concept
complex
gave the tricarbonyliron 9 complexes c13.62; L = i?Ph3' derivatives were prepared also.
(13.6~; L = CO) underwent
acid to give ion
[233].
the first
complex
reaction (13.63)
of
83
OSiMe
3
\P/
OSiMe3
Fe
w3
m3
13.58
13.59
O-BF-
3
/ P
0
-
Fe
mu3
(co)3
13.60
13.61
/\ F 13.62
BF -
4
13.63
Reactions of the T-enyl complexes
[(y5-C6H7)Fe(C0)3
[(y5-C7H9)Fe(C0)3]BF4, [('\~-c?H~)F~(CO)~]BF~, C[(S.l.O)? CgRq]Fe(CO)3jBF4, [(T\~-C~H~)F~(CO)~]BF~and [(q7-C7H7)Moo(C0)3]BF4 with selected anionic nucleophiles have been investigated [234].
References p. 128
84
The l-cyanocyclohexadiene
complex (lj.61L;r(= CN) was
treated with hydrogen chloride and methanol to give the methyl iminoes'cer (13.65). base i;ave
the amide
'Treatment of i;heiminoester (Ij.;5, with (1 j,Si+;
13.64
d = COX. ) and co::aensation with the 2
13.66
13.65
appropriate nitrogen compounds afforded the heterocyclic derivatives Z-(2-cyclohexadienyl-2,2-irontricarbonyl)imidazoline-2, -benzoxazole, -benzimidazole and Z-phenyl-S(S-cyclohexadienyl-S,S_irontricarbonyl)-l,j,4-oxa~iazole. reactions of \-cyanocyclohexadiene
derivative 113.66)
Some
xei?e alao
investigated [235% The symmetrical. 3-methoxy cation (13.67) has been prepared from tricarbonyl(~,-l,~-dimethoxycyclohexa-1,~-diene)iron by treatment with trifluoroacetic acid. The cation (I 3.6’7) was shown to be synthetically eq.uivalent to a meta-methoxybenzene cation OP to a S-cation
of cyclohex-2-enone.
OHe
The prer,mation
cl= 1 0
,
,I
13.57
13.68
‘i3.69
85 of
tricarbonyl(l-cyclohexa -2,4-dienone)iron was also described
and nucleophilic reactions at the l-position of this complex were investigated
[236].
Stereospecific reactions of' tricarbonyl(y-cyclohexadienyl)iron salts, derived from unsymmetrically substituted tricarbonyl(y-cyclohexadiene)iron complexes, have been used to direct the .f'ormationof new chiral centres at carbon and so to define absolute configurations by chemical correlation with the terpenes cryptone and phellandrene.
For example, (lS)-(+)-tricarbonyl-
(n,-I-methoxy-1,3-cyclohexadiene)iron (13.68) has been correlated with (R)-(-)-cryptone (13.69) [237]. The (y-cyclohexadiene)iron complex (13.70; E = CH2), obtained by a Wittig reaction on the (T-acetylcyclohexadiene)iron complex (13.70; E = O), was protonated with fluoroboric acid to give the salt (13.71). Acetylation of the same complex, (13.70; E = CH,), with one mole of an equimolar mixture of AlCl, and Me
I CHCH2COMe
k
BF 4
CC. I' , ‘.r ij Fe (cO)3
13.71
13.70
2
13.73
References
p. 128
COMe
13.72
+
PF6-
86 MeCOCl
gave
three
products,
the salt
(13.72)
(13.73;
(y-cyclohexadiene)iron
complexes
R1R2
of 14, 26 and 4.5%
= =CH2)
in yields
Me0
and the
R1 = lie, R' = Cl; respectively
(CH2)nC0214e
CH
[238].
2
\ (CH& Fe
Fe
(co+
(COj3
13.74
13.75
\
J
13.76
0
v $
13.78
0
CH(CH20H)2 ." ___
0
0
0J
Fe (GO)j
13.79
87
H CH2OH H
13.80
13.81
(y-Cyclohexadienylium)iron complexes have been used as intermediates in the synthesis of azospirocyclic compounds.
Thus
the (r\-cyclohexadiene)iron complexes (13.74; n = I, 2) were converted to the (y-cyclohexadienylium)iron intermediates (13.75; n = 1, 2) by sequential reduction, tosylation and hydride abstraction. The intermediates (13.75; n = 1, 2) were treated with benzylamine and subjected to demetallation and hydrolysis to give azaspirocyclic enones (13.76; n = 1,'2) [239].
In a
related sequence of reactions the (T-cyclohexadienylium)iron complex (13.77) was stereospecifically converted to the trichothecane intermediate (13.78) [240]. Stereospecific cyclization of the (n\-cyclohexadiene)iron complex (13.79) using T1(02CCF3)3 in the presence of sodium carbonate gave the cis-hydrindene complex (13.80) which underwent acetylation and decomplexation to form the product (13.81; Y = 0). A similar cyclization was used to obtain the product [13.81; Y = C(CO,Me),] [241]. A stereocontrolled total synthesis of a 12,13-epoxytrichothecene analogue (13.82) has been achieved using the hexafluoroThe synthetic route described illustrated phosphate salt (13.83). the usefulness of the Fe(C0)3 group for diene and dienol ether protection [242]. The conversion of the diastereoisomers (13.&;
R =M-
P_C02Me) to steroid precursors has been described [243]. Oxidation of the complexes (13.85; oc-cO2Me, OR =K-OH; p-C02Me, OR =B-OH)
References p. 128
was effected with either thallium(II1)
or
+
Me
I I Q a
\
’ *_
,
OMe
PP6-
I;'e
(W3
13.83
13.82
OMe
Me0 Fe
13.84
trifluoroacetate corresponding complexes
or iron(II1)
cyclic
and related
b,k-disubstituted
isomers
the j-exo
zbably
Catalytic
were
by phosphines
readily
and in methyl
gave
the bicyclo[j.2.0]
to the cycloheptatriene
into
[2441. -cyclohepta7 either S-exo or s-end0
direct cyanide
via a metal-assisted
amounts
The latter
converted
tricarbonyl(n,-cyclohepta-
In dichloromethane, isomer
gel to give the
to the tricarbonyl(
of phosphine-substituted
was formed
izing
addition
cation
:,3-diene)iron. gave
compounds
on silica
(13.86 and 13.67).
cyclohexa-2,S-dienones
Hucleophilic dienylium)iron
chloride
derivatives
complex
(13.89).
at the ring
the 5-w
pathway
of acid or base were nona-2,4-dien-B-One
attack
isomer
[2'45].
effective complex
Kechanisms
in isomer(13.66) involving
89
(c0j3 Fe
OR \
I 0-b Me
C02Me
Me
C02Me
13.86
13.85
Fe
Km3 13.87
13.89
References
p. 128
13.88
so vinylcycloheptatriene reactions
intermediates
were used
to explain
[246-j.
The
2-oxyallylcation
2,i+-dimethylpentan-j-one
(13.90),
generated
from
and enneacarbonyldiiron
(13.91)
whose
oxidative
structure
degradation
was
confirmed
of the adduct
13.90
gave
group.
compound
Similar
13.92
were
had
inserted
carried
out with
tricarbonylC8-(4-chlorophenyl)-8-azaheptafulvene]iron tricarbonyl[(N -ethoxycarbonyl)azepine Protonation
with HPF'o, HBF
(v-cyclooctatetraene)ruthenium
/\ 8 I 0
or CF3C02H
‘L.!
PF6-
and (I-arene)-
the corresponding
+
e
0 .d
13.93
of
gave
I RLl
13.94
a
[247,248].
3iron
?omplexes
i I-
The
analysis.
(13.91) with o-chloranil
(13.92) which
reactions
treated
a 1 :I adduct
by X-ray
13.91
the iron-free
carbonyl
2,4-dibromowhen
tricarbonyl(q 4 -cycloheptatriene)iron,gave
with
the
PF6-
[(ij-arene)(l-5-r\-CSH9)Ru]+ cations (arene = mesitylene, hexamethylbenzene or t-butylbenzene) which were isolated as PF6 or BF salts. The mesitylene and hexamethylbenzene species
4
isomerized on warming in organic solvents to [q- arene)(I-3:6-7-q-C8H9)Ru]+. The structures of the isomeric \-cyclooctatrienyl complexes (13.93 and 13.94) were determined by X-ray analysis 12493. Cxidative dimerization of tricarbonyl(T-cyclooctatetraene)iron (13.95) gave the dication (13.96) which was attacked by triphenylphosphine to form the (?-bicyclooctadiene)(r\-bicyclooctadienyl)diiron cation (13.97; R = Ph) and this rearranged to the intermediate (13.98) before undergoing further addition of triphenylphosphine to give the bis-phosphonium salt (13.99). Both triphenylphosphine groups were displaced by hydride on treatment with sodium borohydride to yield the binuclear (I\-cycloheptatriene)iron complex (13.100).
The crystal and
molecular structure of the bis-phosphonium salt (13.99) was determined by X-ray crystallography. Wnen triphenylphosphine was replaced by tributylphosphine then the dication (13.97; R = Bu) gave the bis-phosphonium salt (13.101) which was reduced with sodium borohydride to the (r\-bicyclooctadiene)iron complex (13.102) [250]. The (y-cyclooctatetraene)iron complex (13.95) underwent electrochemical or chemical oxidation to the reactive radical cation (13.103) which was followed by isomerization to the bicyclic species (13.104) and dimerization to the binuclear dication (13.105; L = CO).
The crystal structure of the cation
[13.105; L = P(OPh)3] as the PF6- salt has been determined by Borohydride ion reduced the cation X-ray crystallography. (13.105; L = CO) to the neutral complex (13.102) while bromide ion caused reductive C-C coupling to form the complex (13.106). This last product (I3.106) was converted to the binuclear complex (13,107) with enneacarbonyldiiron Ligand substitution and nucleophilic
[251]. I?eaCtiVity
in
tri-
carbonyl(r\-cyclooctadienylium)iron (13.103) has been studied. Attack by cyanide ion gave the carbonitrile (13.109) and the cyclooctatriene)iron complex (13.110) while triphenylphosphine (Y gave the phosphonium salt (13.111). Methoxide ion led to the -cyclooctadiene)iron complex (13.112) while iodide gave the (I (l-cyclooctadienyl)iron complex (13.113) which was converted
Referencesp. 128
/\ 0
92
”
-
Fe
FejCO)
(GOI3
I-
(CO)3F~
3
PR
13.96
13.95
3
I
p&q
3
Fe(W3
(CO)3Fe
I
13.98
ie(C0) 13.99
PPh3
3
Fe(CO)3
13.97 mu I 3
(COJ3Fe
NaBH
4
13.102
\
(CO13Fe
13.95
/\ \0/
-e
. 6 93
+
+
l’
:
I
*
(W3
NOI
13.103
I
Fe
ma3
13.104 /
Fe (CC1). 2+ 3
Fe
Kxo2L 13.10 ‘5
13.106
I
Fe2(C019
\/ \/ ($3 Fe
Fe
m3
mN3
13.107
References
p. 128
8’
Fe
Fe
\/ \/ m
l__.’
H-
b 13.102
d
94
\3/
PPh3 Fe
Fe
Fe
(CO13
mx3
(cm3
13.108
13.111
13.712
I\
Fe
Fe
Fe
NOI
13.109
13.113
13.110
CN-
:0. , /
‘..__-’
Fe
(Cop
13.114
OMe
95
with cyanide ion to the product (13.114).
Several related
reactions were reported [252]. The electron rich cyclooctatetraene complexes (y4-C8Ha)Fe(C013, (7\4-C8H8)(y5-C5H5)Co and (r\4-C8HB)(\5-C5H5)Rhhave been treated with unsaturated cationic derivatives of rhodium, iridium and palladium to form dimetallic products. For example, reaction of the iron complex with y4-cyclooctadienerhodium tetrafluoroborate gave the cation (13.115).
All the complexes
prepared were characterised by 13C NMR spectroscopy [253]. TsO
H
&I-
Fe
(CO13
13.116
13.115
(y4-Cyclooctadiene)(q6 -cyclooctatriene)ruthenium has been shown to behave as a selective hydrogenation catalyst with some polyenes.
For example, cycloheptatriene was hydrogenated
at room temperature under one atmosphere of hydrogen and it was possible, by variation of the solvent, to form monoenes
[254] -
The rates of solvolysis of the complex (13.1161 and the corresponding free ligand have been measured. The presence of the tricarbonyliron group increased the rate of methanolysis. This was believed to be the first example where iron complexation had increased the rate of reaction at a remote site where there was no possibility of direct metal participation 14.
[255].
[(?+H;)Fe(‘+&~ The ligand-exchange reaction between arenes and ferrocene
has been utilized for the selective complexation of aromatics in petroleum. The aromatics were identified by pyrolytic mass spectral analysis and by thin layer chromatography of the
References
p. 128
96
-arene)(s\5 -cyclopentadienyl)iron (15 exchange reaction.
cations formed in the
There was good agreement between the two
sets of data [256]. L&and
exchange reactions between ferrocene and g-, g- and E-toluidine gave the corresponding (n,-cyclopentadienyl)(q-toluidine)iron cations (14.1) which underwent deprotonation with potassium t-butoxide in TBF to form the zwitterionic These complexes (142) were effective as complexes (14.2). nucleophiles in reactions with methyl iodide, carbon disulphide, acetyl chloride, propionyl chloride and benzoyl chloride. The products (14.3; R = I%, At, Ph) were obtained from the three acid chlorides
[257].
t NHCOR
Fe
Fe
PP6-
6 0
14.2
Ligand exchange in
(+)-1,2-
14.3
(a-ketotetramethylene)ferrocene
(14.4) was carried out in benzene in the presence of aluminium chloride. Retention of configuration occurred and the optically
6;; 0
0
Fe
Fe
14.5
97
active salt (14.5)
was isolated with an optical purity close
to 100% [258]. Ligand exchange has been effected in a series of ruthenocenes (14.6; R' = Et, COMe, H) by treatment with an aromatic hydrocarbon in the presence of aluminium chloride-aluminium
Q 0
Q
The corresponding cations (14.7;&=
powder.
0
RI
RI-
Et, COMe, B;
+
Ru
RU R3
6
0
R2-0
0 R4
14.6
14.7
R* = R3 = H, R4 = H, Cl, Me; R2 = R3 = J34 = We) were formed and these were isolated as the hexafluorophosphate salts [259]. Ferrocene has been attacked by [2.2]paracyclophane in the presence of aluminium chloride and aluninium powder to form
Q
2+
0
Fe
PF6-
0
Fe
2PF6-
0 @ Fe
14.8
References
p. 128
14.9
98
the
(v-paracyclophane)iron Oxidation
of the
with N-bromosuccinimide cation Yhen
(14.11)
cerium(IV)
cation
(14.11)
Oxidation toluene
of
complexes
(I-cyclohexadienyl)iron gave
and the free was
a mixtare ligand
the oxidizing
and benzene
Q
agent
(r\-benzene)(\-toluene)iron
complex
of the
PhCMe2CN
was obtained
as the only product
#‘--
(114.8 and 14.9)
[r60]. (14.10)
(n,-benzene)iron
in the ratio
then a mixture in the ratio with
1:s.
of the 1:l.
ceriurn(IV) gave
[261].
+ CMe2CN
'*__
Fe
Fe
14.10
14.11
The electronic
absorption
(T-cyclopentadienyl)iron mesitylene,
tetralin,
and the corresponding interpreted
14.13) 4
3
biphenyl, neutral
of a series arene
naphthalene complexes
in the
has been
have
of
(T-arene)-
= benzene,
toluene,
and phcnanthrene, been
recorded
(r\-cyclohexadienyl)iron complexes (14.12 13 C NMR investigation. in a
compared
-
9 :'--'._.
2
Fe
(CW3
14.12
where
[262].
Bonding and
spectra
cations,
14.13
and
99 In the tricarbonyliron complex (lL+.lZ)
the Least shielded carbons
were C(2,4) while in the ( -cyclopentadienyl)iron complex
7 were similar [2633. (14.13) C(2,3,4) The I3 N l@B spectra for seventeen (?-arene)(~-cyclopenta-
(14.74; X = H, Me, Et, Pr', But, Ph, OPh, COPh, OMe, C02H, NH2, NH +, NMe2, CN, NO23 F, CL) have been 3 measured and analyzed in detail. The chemical shifts were interpreted qualitatively on the basis of ligand-metal interactions. 13 C NMR spectra were recorded for seventeen polgdienylliron salts
substituted arene complexes,
E(l-arene)i?-CsHs)Pe3PF6 [264]-
r
-4
0
-IR
0
PF6-
cf,
BF 4
Ru
0
14.14 NuCleOPhiliC
14.15 replacement of chlorine in (l-chlorobenzene)-
(~\-cyclopentadienyl)ruthenium tetrafluoroborate occurred when it was treated with methanol, pipe&dine
or ammonia to give
corresponding ruthenium complexes (14.15; R = MeO, piperidino, NH21 [265]. The nucleophiZic displacement of chloride by phenoxides
(34.17; R = H, 3-$ h-Me, 4-Ph, 3-CQ$k,
3-C%, ~-BP)
in the
(r\-benzenejiron complex cations (14.16; R = H, Z-, 3-Me) has been the subject of a kinetic investigation. Hammett e values were determined for the three cations (14.16) as 3.16, -3.55 and -3.01 respectively, The reaction mechanism was interpreted in terms of Meisenheimer-type intermediates
[266].
The azido complex (14.38; X = N3) has been prepared by the chlorobenzene derivative (14.18; X = Cl.) reaction of the ,\6with sodium azide. Pyrolysis in vacuum or irradiation of the complex (q4.18;
x = 83) gave (i\b-aniline)(~5-cyclopentadienylf-
iron hexafluorophosphate
References p. 128
(14.18; X = NH2) together with some
100
+
R
R
Cl 9 Fe
m
6 0
o-
14.17
lit.16
cyanoferrocene. terms
The formation
of a phenylnitrene
of these products
complex
was
explained
in
[267].
The addition of LiCH(CN3)CIJ to the cation (l&.19) gave 5 -cyclohexadienyl)(r\ 5 -cyclopentadienyl)-iron initially a (T\ complex
which
mediate
(14.20)
was oxidized and
by N-bromosuccinimide
then to a mixture
to the inter-
of the cyanides
(l&.Ll)
in the presence
of 6-
3.
[ 263
Photolysis or 2-electron
(14.22)
of the cation donor
ligands
resulted
in replacement
of the
7-E -X y lene ligand with one 6-electron or three %-electron donor ligands. The 6-electron donor ligands were cycloheptatriene, cyclooctatetraene and 2,2-pnracyclophane and the ?-electron Y6donors were trimethyl- and triethyl-phosphite [269]. Irradiation
of
hexafluorophosphate by visible
light
was heated
with
powder
(\,5-cyclopentadienyl)(~6-E-xylene)iron and
gave
[2.2]p aracyclophane
the iron complex
[2.2]p aracyclophane
and aluminium
chloride
in dichloromethane
(14.8).
Jnen ferrocene
in the presence
the dication
of aluminium
(14.9) was formed
[270]. (l&.23; R1 = H, R2 = Me,
The ketones
R1 = Me, R2 = Ph) have secondary Acids
alcohols
were reduced
been
transformed
or pinacols similarly
alcohols.
The electroreduction
organoiron
group
group
rather
chemical
into
by cathodic
to give
reagents [271].
the corresponding
reduction
the corresponding
was activated
and it was regiospecific
than on the ring,
Ph; R1 = R2 = Me;
in contrast
on mercury. primary
by the cationic
on the functional to the reduction
with
OF SgLYCT.&:D ~-~OIq~PL~~S
AMXUAL SURViY COVdRI::G THS YZAR 1981’” GEORG& NARR and BERNARD d.
ROCKETT
Department of Physical Sciences, The Polytechnic, ~~olverhampton
XVI 1LY (Great Britain)
1.
Reviews
2.
General Results
3.
b-p$&pwo)4
4.
kj-CgH6&W+
(i) Formation (ii) Spectroscopic and Physico-chemical
5.
StUdi8s
(iii) General. Chemistry
16
(r\-CsRbf+
24
6.
[(y-C7H7)C~(CO)3]+
7.
(~-CgR~Dfn(C0)3
29
(i) Formation
29
and (C7Ra)Cr(CO)3
(ii) Spectroscopic and Physico-chemical Studies (iii) General Chemistry (iv) Applications
27
30 33 46
8.
Polynuclear (~-C~H~)~~(~O)~ Complexes
47
9.
Carbene and Carbyne (~-C5R~)I?n(CO)3 Complexes
50
IO.
(~-Trimethylenemethane)Fe(CO)~ Complexes
53
11.
(Acyclic-y-diene)Fe(C0)3 Complexes
54
12.
(~-c~H~)F~(C~)~
65
Organic Reactions of SelectedTT-Complexes, Annual. Survey Covering the Year 1980 see J. Organometal. Chem., 230 j1982) 261-374. References p. 128
2 I?.
68
(Cyclic-~-diene)Fe(CO)~ Complexes ii)
68
Formation
78
(ii) Spectroscopic and Physico-chzrnical Studies (iii) iGenera Cnemistry
82
1f.1 .
[(r,-c';j!5)ii'B(?-CgI::,)]f
95
15.
(n,-CsI!s)23u
16 .
(?-!:lc"iiiCo(n-CSEIS)
17.
(y-C53S)2Cn
18.
Cobalt-carbon Cluster Compounds
118
19.
(-~,,-C~iS~)~l$i.
123
20.
(7\-C8Lti)*U
126
and (q-CgES)20s
and
105 107
[(q,-~C$15)2Co]+
111
References
1.
128
Reviews
Jonas has reviewed the chemistry of a1:ali metal-transition metal T-complexes.
Dhis review contained a section on the preparation
of trrnsition metal-olefin 2nd alkali metal-transition metal-olefin complexes from metallocenes, mainly cobaltocene and ferrocene, by reductive elimination of the cgclopentadienyl ligand [I]. F'roboese has revieued the antitumor activity of metallocenes :iatts has reviewed tire chemistry of -cgclopentadienyl, 14‘ r\-arene a;!drelated complexes :,ublished in'lL>*/S(33. Ueeming has presented a brief review of the ruce:itly 7,ublished chemistry ofT-'oonded organometallics Clc3. Eowell has revietjed the chemistry of hydrocarbon-metal 8complexes published in 1979 (51.
The role ofG-T
rearranpme3t
of organotransition metal complexes has been reviewed in the context of organometellic catalysis k4 2.
General Results Several decamethy3metallocenes
decamethglmetallceene
(2.1; M = V, Cr, Co, Iii) and
cations ((1.2;M = Cr, CO, Iii, n = 1; li = ici,
n = 2) have been prepared and their electronic properties studied. NMR, IR spectroscopy, magnetic susceptibility and, in some cases,
3 X-ray crystallography have b-en used to show that the compounds (2.1) and cations (2.2) were D5d or D5h with low-spin configurations. Reversible, one-electron redox reactions have been demonstrated by cyclic voltammetry for the systems:
where PI = Cr, Pi, Fe, Co, Ni
The decamethylmetallocenes were, in general, more easily oxidized $3 to the corresponding cations than were the free metallocenes. and I3C LNR and TJV spectra for several decamethylmetallocenes have . been recorded [7]. r
0
Q 0
2.1
-iT 0
ti M
n+
I
M
1~ 0
2.2
Several complexes of pentakis(methoxycarbonyl)cyclopentadiene, HCS(C02He)5, have been reported. The fully-substituted metallocenes (2.3; PI = Mn, Fe, Co, Ni; R = C02Me) were obtained by treatment of the free ligand with the appropriate metal(I1) acetate. The complexes (2.3) are water soluble and are fully ionized in water. The structure of the ruthenium complex (2.4) has been determined by X-ray crystallography M. The frequencies and forms of the normal. vibrations in symmetry coordinates have been calculated for the metallocenes (~-CSHS)~M, where 14 = i%g, Ca, V, Cr, Mn, Fe, Ru, OS, Hi.. The nature of the metal. exerted only a small influence on the shape of the normal vibrations. References
p. 128
Force constants for the vibration werecalculated [9].
4
CO We
R R
-:l‘r 0
R
R
R
PI
R”
Q 0
I 2
R
R
R
%. 3
2. 4
ryhe -I9 TT2' ..I&?spectra
of the 3- and 4-fluorophengl derivatives of ferrocene, ruthenocene and osmocene were recorded. 'TheTaft equation was used to obtain inductive substituent constants of -0.032,
-O.Qi+Z and O.i\& and reSonance Substltuent constants of
-0.107,
-0.0?7
and 0.095 respectively for the metallocenyl groups.
The fluorophengl derivatives of tricarbonyl(y-cyclopentadienyl)manganese and -rhenium were prepared also and examined [IO]. The cross polarization method has been used to obtain highresolution solid-state '31:323 spectra of fcrrocerie, ruthenocene, biS(r,-benzene)chromium and related sandwich compounis. The shieldin,-,tensor anisotropy reflected the character of the bonding. Xotion was observed in Several of the compounds and has boen used to
assign the shieldinS tensor principal directions
Cl'l* The dynamics of ring rotati.on in ferrocone, nfckelocene and
ruthenocene have been studied by incoherent quasi-elastic neutron scattering.
At temperatures above the 164'K phase transition the
activation energy for ring rotation in ferrocene fell to
0.5 kJ mol-’
T.4 2
(approximately half the lori temperature value).
At
room temperature the n,-cyclopentadienyl rings in nicirelocene behaved the same as in f'errocene but in ruthenocerie they reoriented l.eSS frequently and resembled those of ferrocene below 16b OK [12]. The proton af'finities for twenty organotransition metal complexes including benchrotrene, methylcymantrene, ferrocene, ruthenocene and nickelocene have been determined in the gas phase by ion cyclotron r:>Sonance spectroscopy. The site or protoaation has been determined in several. cases [131*
5
~~icrosolution optical spectroscopy has been used to monitor the fate
of
metal atoms deposited into cryogenic solutions.
i'h0
interactions or iron, cobalt, nickel and zirconium vapours with liganda such as COD and toluene were examined and reaction intermediates proposed on the basis of the optical spectra obtained [14]. A theoretical study using ISit SCF EO calculations has been carried out in order to make comparisons between the cyclopentadienyl, borabenzene and benzene ligands in sandwich complexes of chromium, manganese and iron. Ground state differences were found within both the borabenzene series and cyclopentadienyl series of complexes and also between th.e two series.
The differences
were rationalized in terms of a simple ligand field model
[Is].
The Thouless instability conditions in a series of polydecker organometallic sandwich compounds have been investigated by semiempirical IliDO calculations. Hartree-Pock fluctuations of the singlet, non-singlet and non-realtype were found. The PeaSOns for the various instability conditions vere analyzed [I61. 3.
w@~lv(co~ic The solid state structure OS the (y-cyclopentadienyl)vanadium
complex (3.1) has been determined by X-ray crystallography. In solution, IR, 31P and " V NM3 spectroscopy showed that the molecule was fluxionaf down to 200 OK [17]. The photoreactions between tetracarbonyl(?-cyclopentadienyl)vanadium and the ligands
Ph2iGB2&Ph2 (6 = P, As, Sb) have been
investigated. The complexes (3.2 and 3.3; & = P, As, Sb) were isolated and investigated by 51V XhR . The crystal and molecular
3.1
References p. 128
6
myJ \ Ph$TX2EPh2
3.2
3.3
was determined by X-ray analysis structure of (?-Cj:'~)V("O)?ns2Ph4~
bl.
The binuclear dkradical (3.i~)was obtained by coupling of bis(v-benzene)vanadium,
the product was characterized by 3H
spectroscopy [193.
3.4
The condensation of chromium vapour with phenyl- OF Q-tolylferrocene produced l;he bis(n,-arene)chromium complexes (,$.I;ii = il or Ke) respectively
[Xl].
Fe
Cr
Fe Ph
LL.2
4.1
Treatment of hexacarbonylchromium with I-phenyl isophosnhinoline produced the bis(tricarbonyl_chromium) complex (4.2) [Zl]. Reaction of tricarbonyltris(methy1 cyanide)metal complexes with 4-R-X3-arsenines and 2-aryl-4-R-X3-arsenines gave the corresponding tricarbonylmetal complexes (it.3;R = Ph, cyclohexyl, t-Bu, Et) and
(4.4; R = Ph, cyclohexyl, t-2;~; &I = Cr, ho, Si)[22].
The preparation of some oligomeric (y-arene)transition metal tricarbonyl complexes has been reported [2_1], Steroidal hormones containing benzene rings, such as estradiol, estrone-j-methyl ether and estrone have been treated with chromium, molybdenum and tungsten hexacarbonyls to form the tricarbonylmetal complexes, such as the tricarbonylchromium complex (4.5). kinetics of formation was monitored
'The
[24].
Benchrotrene and related complexes (4.6; ii. = Ii, l\le, N = Cr, NO,
W)
have
been
obtained in high yield by heating the free Ph
MO
umg
ti
MN3
4.4
Referencesp.128
OH
4.5
ligand
with
ii.6
the appropriate
the autoclave
with
The synthesis derivatives
hexacarbonyl
reported. induced
.i“hemultistep
achieved
by using
carbonyl
groups.
The corresnonding
complexes
The reaction chromliium produced products
Cr
4.7
reaction
for replacement
labelled
was
of' the three
thiocarbonyl
X = S, Se) wel'e obtained
of trivhenylbismuth the lT-complexes (4.8, !;.9
with
and in similar
triamminetricarbonyl-
(q.8, 4.9 and 4.10;
and 4.10;
(=+
7 (140)
'C in
[%6].
reactions
Similar
(Ll.7;
excnange
atom >0 13 C enrichment
and>90
13 CO as the reagent
selenocarbonyl
at 150-170
picoline or thiophene catalyst [&I. of 13 CO labelled benchrotrene and benchrotrene
has been
was photochemically
metal
a pyridine,
lWh2
Cr 2
cx
NW3
4.8
PI = Bi).
1~~= Sb) were obtained
4.9
by
4.10
treatment of the chromium complex with triphenylantimony in the presence of boric acid [27]. 4.
(ii) Spectroscopfc and Physico-chemical Studies
The crystal and mo3.ecular structure of the (r\-naphthalenefchromium complex (4.11) has been determined by X-ray crystallography. The molecule exhibited an octahedral. arrangement about chromium and Cr-naphthalene bond distances were similar to those found in the corresponding tricarbonyl complex. The structure of a related (~-phenant~rene)chromi~ complex was also
had a short Cr-P bond.
reported [28].
The crystal and molecular structures of hexaethy~benzene and of its tricarbonylchromium, tricarbonylmolybdenum and dicarbonyl(triphenylphosphine)chromium complexes have been determined by The structure of the tr~pheny~phosp~~ne complex
X-ray analysis.
References p, 128
10
differed from the others in that all six of the ethyl groups were arranged such that the methyl moiety projected towards the uncomplexed side of the ring and the molecule assumed a staggered conformation [293. The crystal and molecular structure of the dicarbonyltrifluorophosphinechromium complex (4.12) has been determined by0 X-ray crystallography.
The chromium-phosphorus distance, 2.132 A
was the shortest found to date and suggested that the trifluorophosphine ligand was a good ?r-electron acceptor [30]. The structure of the tricarbonylchromium complex (4.13) has been determined by X-ray analysis. In the lattice the mo1ecuI.e was distorted in that one of the Cr(C0)
3
groups could be on either The geometry
side of the phenyl ring to which it was bonded.
around the tin atom was approximately tetrahedral
4.13
[31].
4.14
X-ray crystallography and NIviRspectroscopy have provided strong evidence that the fl-phosphorin)chromium complexes (4.14; R' = Ph, CHe3; R2, R 3 = Ke, Et, CIVie UMe, %2t2, 5')have a 3' zwitterionic structure [32]. The benchrotrene complexes (4.15; X = E-He, o-Pie, e-OMe, p-F, E-CI and 4.16; R = O-Me, E-he) have been prepared and the IR and 'I-i WR spectra recorded and interpreted. Substituents in the uncomplexed benzene ring in complex (4.15) had little effect on the stretching frequencies of the tricarbonylchromium group. Some electron delocalization between the two arene rings was indic;;ed by the NKR spectra (331. MO NIIE spectra of LYIo(CO)~ complexes (L = I-cycloheptatriene, ?-mesitylene, q-o, m, and p-xylene, l-toluene, n,-cyclopentadienyl) have been recorded and discussed. The chemical shift was related
(CO$
4.16
4.15
to
HI@ m~~ybd-m-m-z~~~~ AS part
of
nonequivalence
methyl
the
crystal
cation
characterized
with
with to
respect
g-Be,
J@3, been
the anion
E-O-Se, prepared
and investigated delocalization
References p.
to
interpret
The radical have
128
in has
S-He the
been
isopropyl
I$
pp;
potassium
unpaired
= Ii;
cations, of
the
by
X-ray
units
group.
of
gauchewere
[?$I. (4.18;
R’
= H,
R2 = +*-he,
j.@3
the
cOW?lexes
The results density
or
The results
R3 = H,
reduction
benckro-
were
trails-gauche
colnplexes
electron
magnetic
structure
MM? shifts
bsnchrotrene
by
of
determined
either
diastereotopic
j+l,
origin
eonformation&.
g;roup
bY !.ISR spectroscopy. of
the
iso-propylsulphonium
and molecular 14.17)
the
[3i;j.
into
groups
Two alternating
crystaifography,
used
S~XWI~~~
an investigation of
tre~esul~honi~
gauche
bond
over
parent
f
confirmed the
ligand
system
12
0
R
COCH,CH2CH3 i
p Cr
w3
m3
4.19
4.20
Dipole determined
moments
and molar
for a number
Lerr
of benchrotrene
C OPle, CO2ILle,Oi,Te,iTEz, 1;HIze,ilKe2). evidence
from
conformations plexes
(!+.liJ)and t'ne free
In the mass
spectrum
hydro:;en transfer deuterium
processes
labelling
Iropylene
elimination random,
the decomposing from
ion.
0
occurred
Pm3
4.21
to_:ether ;;ith
that t.le .,,referred
complex
and these
goup
the com-
In another
(!.,.cC)several
were
studied
by
in the I-, 2- or j-position.
specific
on the pressure
(i:Aciaffe..'ty rearrallgerflent) of carbon mollO:~ide at
rearrangement
hydrogen
was
the I-posi.tion of the nro;oyI croup; to the ester spectra
of fL)ur '0e;icilrotre:le
(!1..21;PI = Cr, X = Okle, OBun,
x
C02he,
C02sun)
and of the
7 0
?Pi
(k.19; R = CHO,
results,
silmf.15rin both
[30 of the chromium
was either
depending
been
ligands
carbonyl c?rbon atom [36]. The electron impact mess complexes
were
of the "ropyl
or mainly
transferred
complexes
These
I;? sr:ect:-osc,o_-y indicated of the substituects
at 509 nm have
constants
Cr (COj3
4.22
4.23
R
13 analogous tungsten complexes (i&.21;PI = w, x = Op;;e, oaun, COpBun) have been recorded and analysed in detail to give complete
CO b& 2
fragmentation diagrams.
Differences between the tungsten and chromium complexes were attributed to the stronger electpophilic character of tungsten and its tendency to attain higher oxidation states [39]. The mass
Spectra
of negative ions formed by the dissociative
electron capture (Jd,'c) Of I-complexes have been recorded and interpreted. Ampg the complexes ezamined were (q'-benzene)-, (q6-indene)-, (n,-fluorene)- and (7 -azafluorene)-tricarbonylchromium. 'The[A-H]' ion from (\6 -indene)tricarbonylchromium underwent a process of recoordination of the chromium atom from the benzene to the cyclopentadienyl ring [40]. I"iassspectra of the benchrotrene negative ions (4.22; X = R, Cl, F, I, Otie, ;JKe2) obtained by DtiC have been obtained. 'The first maxima of the resonance of the ions [h-CO]- was shown to have a linear dependence on the Hammett CP constants [41]. The favoured conformations in the gas phase of several L = CO; benchrotrenes such as [4.23; R = CO$ie, CH(CNej)2, COI'ie, method and R = C02Me, L = CS]have been determined by the A:R,L compared with solid state conformations obtained bY X-ray crystallography.
The conformations were similar in most cases
[42 3. Kinetic
isotope effects have been determined for the sodium
borohydride and sodium borodeuteride reduction of (?-indanone)tricarbonylchromium complexes (4.24) with substituents on carbons = 2.46 was found cghenR1 = H, 2 and 3. The maximum effect &/kD R2 = exe-tie and this corresponded to a shift of the transition R2
0
RI
0
P+ Cr (co)3
4.24
References
p.
128
14 state from hindrance
a late
to an early
position
by increased
steric
[lc3].
_$:~ro~~en-dcuteriwriiexchan[Je in the benchrotreiie carn;)lexes
(1$.:‘3;
R z B,
Lr = PPh3,
ferrocenylPPh2,
.
Rate
constants
demonstrated ligcnd basic
!%Iasa stroqer media.
the complexes
electron
Only a small (I;. i3;
CO) has be,:~.studied
that
donor
in
determilled f'or exchange the farrocenylPPh
2 the PPh_ ligand in 3 in the exci?an,,erates for
than
difference
l? = H, L = ferrocenylPFh;J,
CO) were
observed
[4 3. Rydrogen-deuterium
(ir..23;
exchange
in the bcnchrotrene
complexes
11 = Ph, PhCH,,
PhCH.CIi,, PhCO, PhO, L = CO, PIh3) in 2 stvdied and rate constants obtained. 111 i;he
Cb'3C022 has been complexes
(!+.Tj; L = PPh
no effect
on t‘ne rate
reaction
positions
)
the
in the free binuclear
in
L = PPh3) had “he
3
the
coordinated
similar
reduction
chaq;e
in ring
areL?es. ligands
reactivities
The _ o- , m-,
(;1..23;
[hi].
of
Jotassium
borohyaride
r>ro;;anolor methanol ii. iso-,,
or
gave
the corres ,onding endo-alcohols
(4.26).
R4
NaBH,,/i-C,H,OH iG3H4/CH30H/H20
-
Cr CO'~'CO co
4.25
to the same n2d E-
for the complexes
by sodium only
substituei.t inad
of excl?an(:e, in ohars contrast
4.26
I’he [email protected]
15
w C02H
0
0
R
CP
Cr
(CO+
4.27
(cO)3
4.28
0
4% Oo
0
CP
CP
(COj3
hm3
4.29
ligand was removed auantitatively from these complexes to give cis- and trans-indanols [461.
The
optically active diphenic acid complexes (+)-(4.27;
R = H, I%) and (-j-(4.28;
R = C02H) have been obtained by resolution
using the cinchonidinium salts although enantiomeric purities were R = CHO) underwent kinetic resolution only G8$. The aldehyde (4.28; with a chiral lithium aluminium hydride complex to give the aldehyde (+I-(4.28; R = CHO), the alcohol (-)-(4.28; R = CH2OH) and the lactone (4.29). The optical yield was 33%. The CO spectra of the optically active products were obtained and used to assign the chirality by comparison with benchrotrene complexes Of known absolute configuration [471* The methoxybenchrotrene complex (4.30) underwent regiospecific lithiation at the k-position and then electrophilic substitution References
p. 128
16 with
cer'oon dioxide
the Li-substituted reactions
to give,
arene
:~rererzoorted
after
(q.jl)
in 91% yield.
4.31
(iii) General
Chemistry
'The electrochemical complexes (4.32; 2 R = He, Okie, 2)
oxiJation
of the tricarbonylcnror~iurn
I?’ = ,,3 = pJ, iI2 = ii, OPie, and (1~.33; .?I = ft3 = Iale,
7 R” = Sikre ) gave stable cations on the cyclic 3 Oxidation of the mono-cor~~>lc.;~:sl4.33) SCale. while
the bis-complexes
stability electron phengl
of the cations
(h~.j:j)gj,avestahlo rias increased
= H, voitametric
gave
time
stable
dications.
cations
i'he
by the introiluction of
dona.tinp; ;;rsoupsinto the (?,Q and 6 !,ositio:.s of the
rings
A series isocyanide
..ieve:qal r>olated
[IJ.~].
4.30
4-
demetalrtiorr ar:d methylation
[1_1_9]. of chromium
li~;ands (j+. 34;
complexes R1 = CO,p,
containin:; functionalised Oi,re,rule,22,
CfDre,, CIsre3, .~
1ccn
)
MeOH UV
Scheme 4.1
4.35
WI"ie2,R2 = 0, no, E-W, 0, E-pie, R3 = Ph, FlNe2, O&t, SEt) has been prepared (Scheme 4.1). The manganese complex (1~~3.5)was prepared similarly.
Infrared and mass suectroscopic studies showed that
the Presence of a carbonyl group M to the nitrogen resulted in the ligand being a better electron acceptor than CO [$I]. Ultraviolet irradiation of the tricarbonylchromium complexes [k.36; n = m = 0; n = 2(2,3-Ne2), m = 1,2; n = 3(2,4,6-b&3), m = 2,3]induced intramolecular cyclization to produce the corresponding dioarbonylchromium compounds (4.37') [sl]. Rj
=
Irradiation of the tricarbonylchromi~ complexes (4.38; = H3 zz H, file; I$ = Rz = Ne, R3 = CK20W, CH,CH,OH) with
$
CR2=CRCRR40R5
(where R4 = H, CH2CH2Ph; Rs = H or allyl) gave the
correspondzing cationic ~-al~y~chromi~ complexes (4.39) [sz]* uv irradiation of benchrotrene with ally1 alcohol and its derivatives in the presence of hydrofluoroboric acid gave
References p. 128
18
Men
9-
(CH2 lrn7
(CO)
F-2
cr./
(CO) 2
3
c /
He
4.36
4.37
(v-erene) (q-allyl)chromium l,j,s-Me3, were
3,5-Me2,
obtained
cationic
compleses
(ib.!~G;;I1 = OH, H,
Cfi2OH; R2 = H, CI-:,iCli2Ph) , Similar
by cleavage
of chelate
dicnrbonylchromium
complexes complexes
such as the benchrotrene
(4.41) and by proton
cleavage
simultaneous
irradiation
of ally1
benc'nrotrenes
as the ether
(ic.42).
Several
substituted
related
reactions
were
with such
re:lorted
[531. A kinetic study of the reduction of the T-acetophenone complexes [I+.;'?; d = ':OPie,L = CO, CS, P(9Ne)3, P(OPh)3, PPh3 PBu3]by arene
of
sodium
borohydride
has been
ligand
>Jas controlled
carried
electronically
out.
, ,The reactivity
by the
Cr(ZO)2L
[54].
group
The rate chromium
b 0
of deprotonation
complex
(4.43)
of fluorene
by potassium R1
has been
-
+
R3 BF -
4
R2
Cr
mN3
4.38
and its tricarbonyl-
hydride
4.39
determined.
19
CH20CH2CH=CH2
CH2 \ 0 (C012Cr I / CH2=c~
4.40
4.41
/ CH
Cr 2
w3
4.42
'H and I3C spectra showed that for the anion generated at -20 'C the Cr(CO)3 group was bound to one of the benzene rings but when the anion was formed at room temperature the Cr(CO)3 group wss bound mainly to the cyclopentadienyl ring [5's].
Cr (co+
4.43
=H;
Treatment of the tricarbonylchromium complexes (4.44, R' = R2 R1 = H, R2 = Me ; R LR2- Pie) in dimethylsulphoxide with
potassium t-butoxide followed by condensation with an aldehyde R3CH0 CR3 = H, Ph) produced the corresponding alcohols (4.45).
The
strong electron withdrawing character of the Cr(COJ3 group had enhanced the reactivity of the benzylic position towards attack by the base [56]. The reaction of benchrotrenic ketones with Grignard reagents was studied.
References
p. 128
Nixtures of secondary and tertiary alcohols were
20
;i 7-
I
R'
0
9-
CH
0
1
RZ
Cr
Cr
(W3
wa3
IL.44
4.45
formed and a mechanism of the secondary metal
Cr
NoI
atom
was proposed
alcohols.
been
in hy:iroy;en transfer
ketallation
lithiated
to account
'This involved
The tricnrbonylchromium have
4.46
of the
[57]. (!;_.iiC,;
complexes
with n-butyllithium
of the substituted
for tile formation
participation
arene
at the --ortho-positior:. The lithiated a series of electronlliles ~8 .
‘i
=
if,
Oi?e, F, Cl)
at low temperatures.
complexes
occurred
intermediates
we?e
exclusively condensed
with
the tricarborlylchromium of ii:R(:ij)U!j" :;ith '
The rnaction complex after
(k.47)
oxidative
has been investigated. removal
i'he major
of the tricarbonylchromium
product group
obtained (Scheme 4.2)
CM
CH
I
3
LiCHCN
11.47
Scheme
4.2
21
corresponded
to
nucleophilic addition on an arene carbon atom
which was in an eclipsed position with respect to the carbonyl group of the Cr(CO)3 unit of the most stable conf'ormer[S9]. Treatment of tricarbonyl(~6-1-methylihdole)chromium with n-butyllithium-tetramethylethylenediatnine followed by ethylchloroformate produced the 2-ethoxycarbonyl substituted product (4.i48; R = C02Et) in good yield.
Lithiation of the Z-substituted indole
4.4%
complex (i+.48;
4.49
3 = SiILIe3) followed by condensation with ethylchloro-
formate afforded the 7-ethoxycarbonyl derivative (4.49)
2s
the major
product together with some tricarbonyl(\6-4-ethoxyycarbonyl-l-methyl2-trimethylsilylindole)chromium
k4 The reactions of (~-benzene)dicarbonyltriphenylphosphine-
chromium with aprotic acids, for example mercury(I1) and tin(IV) chloride, have been investigated. Complexes were formed at the chromium atom which was the position in the molecule with the
(MeIn
4.50
References p. 128
22
i'he II? s;)ectra of the czmy)lexes sho;red high
hi,ghest basicity. carbonyl
frequencies
'The chromium
[61].
complexes
(2,&,6-rle3)] h ave been
Cr(CO)j
of the corresponding
in ;:ood yields or
[q-l
triethylamine
c!ny ri-1;;
L = _ o-31' u6 H ii0) have (~;_.;land i_1_..52;
by the reaction
,j,~-~ie~CbH3CI:~CHZDE]Cr(CO)j folloyred by ultraviolet
:;ith Li'Cl aild
irradtation
reagerits gave
the chiral
n = 2, R = Ile, Bu; n = 3, 2 = he
4.53
[63].
4.5s
Treatmellt of the brid{;ed benchrotrene :rith alkyllithium
been
of [l-l,j,S(~uC~~,_~~H~)~CcHj]-
14.51
where
without
[62].
The chromi.uun complexes prepared
by treatment
(4.50; ;i = F, PhO) !%rithphcnyllitI;i~m
complexes cleavay;e
[i$.";O;Ii = l'h; n = 2 (_3,5-Lie,),n = 3
obtained
complexes amines
b41.
(ic.33; n = 2, 3)
Ph(CH‘~)ili,~rh,:fiPh,
23
Cr
(cOLj
4.5s
4.54
The reaction of benzylcarbenium ion with nitriles to give amides was facilitated by stabilization of the carbenium ion through complexation with the tricarbonylchromium group. Thus the (r\-benzylalcohol)chromium complex (14.54) was attacked by the nitriles, tiCN, where R = Ke, Pr, CW=CFi2, CH2C1, Ph, PhCHZ, 21v,e.C6H4,to give the corresponding amides (4.55) [65]. The charge-transfer comples formed between t;ricarbonyli7j[2.2]paracyclophene)chromium (4.56)
and
1,3,5-trinitrobenzene
in It was concluded that
1,2-dichloroethane has been investigated. there was direct interaction of the 1,3,5-trinitrobenzene with the chromium d orbital [66].
S
Ph
4,56
References pr 128
4.57
24
Senchrotrene
in ace';onitrile IJas attackeLi by 2 nitromethar,e to
lricarbol?yl-cllromium, molybdenum
and -tun;:ste:: Gor~ple;tes of . 1 -oxides have been o;;idizeu with
1 -alkyl-3,5'-diphScnylthiabenzene
IIO+PF6- in dichloromethane dicarbonylnitrosyl
at -76 'C to give
the cationic
[&.57; 1.1= Jr, iio, d,
complexes
CE(SiiGa3)2; T4 = Cr, ii = $ie, A,
CiI,,CH;;lPh, JH,&Le
i? = ~.;(c;h’.P11). 2 ii
] [uo, 693.
i3enchrotre: es bearin,? one, twg or tnree'.metboxy _,rOU')SOil the b.,nzene ring of
methyl
were
sorbate
Y'he reaction of an
effective
to methyl of furan
deac:ivated occurred
with
after
twelve
hours
as the major
:',!J,b-triphenyltriazine
insignificant
compounds
were
(5.1 ),
In a similar amounts
isolated
The structures
produced
was virtually
chromi'um vapour
product
reaction of cationic
together
gave bis(r\-
~itn
some
by cyclotrimerization of bromobenzene
of
;-Jithchromium
bis(?-arelie)chro:-Lila
[??I.
of bis[y-I,&-(trifluoromcthyl)benzer:e chro;Lum 3 heve been
(t:ifluorom~~thyl)benzene]chromium
1
with
formed
bis(y-1,3-(trifluoromethyl)benzene
‘> .
as catalyst
,Tliocatalyst
and up to 150 a1;cylatj.W: events
of benzonitrile
benzo~itrile)ckromil~
in the l)resence
[711*
per molgbde:,um atom
benzonitrile.
compound
and %,5-di-t-butylfuran.
The reaction
only
[TO]. t-butyl chloride
(y-2rene)tricarbonylmolybdenum
z-.t-butylfuran
for ',:henyCPOge:!ctiOn
catalysts
hexenoate
5.2
3chromium, and bis[q-l-cnloro-jdetermilled by A-ray
25 analysis.
The results suggested that the CP3 group did not behave
as a strongly C-electron-withdrawing group and that the polar effect of CF was a "through space" rather than a "through t'nebond" effect [73].3 The heats of thermal decomposition and iodination for the bis-(q-benzene) complexes (5.2; M = No, W) have been determined
+
by microcalorimetry in the temperature range 520-523 OK.
'The standard enthalpies of formation at 25 'C were obtained as 235.3 and 2'42.2kJ mol-' for the complexes (5.2; M = No, W) respectively. Netal-ligand mean bond dissociation enthalpies were derived as 247.0 and 304.0 kJ mol-' for benzene and toluene respectively [74]. Hindered rotation about the metal-ligand bond in the chromium complex (5.3)
spectroscopy has been studied bylH and 13C Zl\iR
9 0 -6-c 6 0
0
Cr
0
5.3
[75].
Cr
0
2
5.4
The redox reactions of twenty bis(?-arene)chromiu
complexes
have been studied via the rotating disc electrode technioue in dimethylsulphoxide.
The half-leave potentials correlated well
with the meta-substituent constants.
It was concluded that the
electronic effects of the substituents were largely transferred to the metal atom by an inductive mechanism
[741. Bis(I-ethylbenzene)chromium has been treated with hydrogen
peroxide in ether or methanol. A yellow solid was isolated and ESR spectroscopy showed that there were peroxide linkages present [771. Bis(r\-benzene)chromium was oxidized by treatment with bis[tris(pentafluorophenyl)germyl] mercury in glyme to give the salt (5.4) in 95% yield [78]. The lithiation of bis(n\-benzene)chromium followed by treatment with dimethyldisulphide gave the r\-methyltlniobenzenederivatives References
p. 128
26
(5.5;
R = Ii
and S&e).
derivatives
and
T‘ne reaction with
The -SH spectra of the r\-methylt:iiobenzene corresponding radical cations were determined.
their
of bis(\-methylthiobenzene)chromiuim
tctracarbonyl(q-norbornadiene)molybdenum
reolacement
product
interconversion
0
(5.6) which
at room
ra:!icico:~formationaI
[791*
(I> / 6 SMe
R
0
i>
The
0
self-exchan{;e
(?6-arene),Cr/
rates
have been
measured
technique.
Cyclic
It was concluded
transition densities
state.
accounted The
of
the electron
mechanism
oligomerization
activity
of the chromium
in the exchange
the electron ei'fects and rates
[oo].
in the presence diphenyl,
as catalysts
has been
and two defluorotrimcrs
were
'The relative
order
of oligomers. complexes
was:
>bis(q-bil,henyl)-
has been used
of perfluoropropylene
of
bis(r\-I ,3,5-trimethyl-
>bis(q-benzene)chromium
Bis(?-benzene)chromium
proceeded
( arene = bonzene,
>bis(q-hexamethylbenzenejchromium
oligomerization
that
by inductive
hexamethylbenzene) trimers
in the mixture
benzene)chromium chromium
Dimers,
t'ne one-
complexes.
reactions
of perfluoropropylene complexes
line broadening
by the side to side
indicated
affected
for the variations
l,j,S-trimethylbenzene,
identified
exchange
and probably
were
= toluene,
to investigate
[($-arehe),Cr]+
All the results
chromium
in the
and chlorobenzene)
spin resonance
of a series
of bis(y-arene)chromiu
investigated.
(where arene
b:as used
that
parameters
ethylbenzoate
voltammetry
sphere
about
systems
biphenyl,
by an electron
reduction
by the outer
and activation
[(T6-arene)2Cr]i
methoxybenzene,
electron
Plot
SMe
SMe
benzene,
\
CP
Cr
these
underwent
temperature
(5.5; ;i = .5&e) ;;ave the li:,and
["I]. as a catalyst
to dimers
for the
and trimers.
One mole of the complex was effective in converting 50 mole of the monomer 6.
[82].
[(q-C+17)Cr(CO)3]+ and (C7R4)Cr(CO)3 Desilylation of the eycloheptatrienyl complex (6.1) produced
the binuclear cycloheptatriene complex (6.2; I4 = Cr) [83].
SiMe3
om3
6.1
6.2
Ultraviolet irradiation of tricarbonyl(y-1,3,$cycloheptatriene)ChrOmium with the monosubstituted fulvenes [6,3; R1 = H, R2 = OCOCH 3; R’ = H, R2 = W(Me)2] gave the corresponding dicarbonylchromium complexes in the exo- and endo- forms (6.4 and 6.5).
The disubstituted fulvenes (6.3; R' = R2 = ONe , R1R2 = -SCH CY S-, RI = Me, R2 = Pin)produced the corresponding dioarbonylckbsium
derivatives
(6.4).
A similar reaction with
cycloheptatr~enyl}chromi~ the f'ulvene C~~~=~I~~~e2 produced the {P,~complex (6.6), the product of hydride transfer from the cycloheptatriene to the nitrogen atom of the fulvene [s4 J. The crystal. and molecular structures of the (I-cycloheptatriene)molybdenum and -tungsten complexes (6.7; lip = NO, X = Te; )I = g, X = Se) together with the dimolybdenum complex, (?-C7"?)llio(r-SePh)3I~o(C0)3, have been determined by X-ray CrystallOgraPhY. Bond lengths and bond angles were reported [85]. Tellurium dioxide was sctivated by evaporation in a metal evaporator and treated with the molybdenum complex (6.8). Reaction occurred to produce the first Te02 insertion product (6.9; H = Te). Sulphur dioxide and selenium dioxide were inserted also into the molybdenum-carbon bond to give the dicarbonylmolybdenum complexes (6.9; I4 = s, se) [86]. References p. 128
28
6.3
6.L.i
cw R2
‘-_
?-
bm2
+
0 I
-
M
6.7
0 0
M02
\
(C0j2XPh
6.6
.-. 9 MO-MMe
NHN14e2
RI
6.5
6.8
0
r--7
0
w
No-PhO_-Me
6.9
29 The tropylium complexes (6.10; $1 = Cr, No, IJ)were coupled by treatment with carbonylmetallates, for example,
~(~-~~~~)~~~o(co)3~and [HB(CO)~]-, to give the corresponding bis(2,&,6-cycloheptatrien-I-gl) complexes (6.2; M = Cr, MO, W) [o7].
Jo
Q 0
M
um3
6.10
The manganesetricarbonyl complex (7.1) was formed from cyclooctatetraene and(PE~(C0)4]3. This dehydrogenative transannular ring closure Of cyclooctatetraene was rationalized in terms or a disrotatory eleetrocyclization of a cyclooctadienyl moiety
[GO].
7.3
7.2
7.3
In an investigation of the formation and thermolysis of tetramethyldiphosphine bridged carbonyl complexes the cymantrene derivative, (I-C~H~)~~(CO)(~-~~~~PPW~~)C~(C~)~, was obtained [69]. Some cyclopropane derivatives of cymantrene have been prepared from the corresponding pyrazoline complexes [90). Several reactions of the mixed cobalt-manganese complex (7.2) Phosphorus and sulphur ligands as reagents
have been reported.
gave methy~c~antrene
and a cobal% complex
[5X].
30
Bromo~langanesepe~tacarbony~ has been attacked by Z,4-pentadienyltrimethyltin in boiling TEF to form tr,icarbonyl(15-pentadienyl)manganese
(7.3) in 52)" yield.
This complex was an open
analogue of cymantrene, it decomposed KLowly in air in the solid state
[92]. (ii)
7.
Spectroscopic and Physico-chemical Studies
The crystal and molecular structure of cymar!trene has been reexamined by X-ray analysis.
,I'he results indicated some localized
C-C bonding rgith bond distances in the ring between I.400 and ? ,439 8. Vibrational studies on cymantrene :'lso supported a breakdo>m of the fivefold symmetry of the ring outside of the crystalline environment [933. The crystal and molecular structure of the cymantrene Schiff base complex (7.4) has been deternlined by X-ray crystallography and the absolute configuration confirmed as S, the kn and &l atoms were trans with respect to the plane of the cycIo:?entadienyl ring
[941*
7.4
7.5
Dimethyldiazomalonate combined with the TI;F complex of cymantrene,
(I-C&)Rn(CO)$%F,
to give the diazoalkane complex
(7.5). &Bay crystallography demonstrated that the complex contained a monodentate diazornalonate group bonded through the terminal nitrogen and with the diazo group bent at the central nitrogen [9.53. The crystal and molecular structure of the cymantrene analogue (7.6) has been determined by X-ray crystallography. Korbornadiene was coordinated to manganese in an exo configuration and was a two-electron donor. The manganese-bridgehead mothylene hydrogen distance was 2.97 A" and indicated a lack of CH+**Kn interaction Cyclooctatetraene attacked the cymantrene complex (7.7) to
[96J.
31
form the (y2-cyclooctatetraene)manganese complex (7.b) the structure of which has been determined by X-ray crystallography.
Analogous
0I 0
Mn---(oW2
\ I
H & H
7.6
compl.exes containing \2-oycloheptatrien% and y2-cycloocta-1, 3,6triene were also prepared 13973. The crystal and molecular structure of the (y-cyclopentadienyl)manganese complex (7.9) has been determined by X-rag
Q
Q 0\ /
0
0
I
ml
Mn-O 3
(W2
(OC)2 /
7.8
7.7
crystallography.
\
The metal atom was sandwiched between the y-CSHs
and the y-CsPH2. Ph3 rings [98]. Gas phase He I, He II and Mg Kocphotoelectron spectra have been recorded for the complexes r?-CgH5_n(CH3)n]M(C0)3 where n = 0, 1, !? and Iv!= En, Re, The influence of the methyl groups was monitored by the shirts in both COP% and
ionization energies.
The magnitudes of the valence ionization energy shifts were relativeIy vdenc8
large which indicated a considerable change in the electronic
References
p. 128
32
0
0
0
Cr
(CO)..CS
z
;: Mn
mp
.F'h
7.10
7.9
I.11
structure of these compounds. It was concluded that electronic effects were as important as steric ef-i'ectsin determining reactivity differences between substituted and unsubstituted q!-cyclopentadienyl complexes. It was concluded also that considerable rhenium to carbonyl Tback-bondin g occurred [99]. The Re I and He II valence photoelectron spectra of the complexes [~-C;I;5_n(C~-I~)n]I.ljll(:10)ZL where n = 1, 5 and L = CzHii, c3H6 have been recorded and interpreted.
It was found that the
ionizations and stability of the complexes were sensitive to the geometry changes that arose due to the introduction of the olefin. These distortions were associated with a lower carbon-carbon bond Strength and an increased metal-olefin bond strength through increased T-donor/T"-acceptor
interactions
[100].
Gas phase core electron binding energies were obtaLned by an X-ray photoelectron spectroscopic study of a series Of thiocarbonyl complexes which included the chromiUm and manganese compounds (7.10 and 7.11)* The binding energies of the metal atom and the carbonyl grouts was approximately constant when one of the carbonyl groups was replaced by a t;:iocarbonyl ::;roup. It was concluded that the electron distribution within the complex was 1arTely unaffected by the change in the ligand. The greater donor character of -the thiocarbonyl ligand being compensated for by an increase in back bonding [101]. The mass spectrometric fragmentation of thirteen monosubstituted (y-cyclopentadienyl)tricarbonylrhenium complexes has been examined.
33 In general the complexes underwent decarbonylation, dehydrogenation and breakdown of the cyclopentadienyl ring
[102].
The IR and Raman spectra of phosphacymantrene and dimethylphosphacymantrene and liquid states.
(7.12; R = H, Me) h ave been recorded in the solid The spectra of the corresponding deutero
complexes have also been obtained.
A complete vibrational assign-
ment has been made and has shown that the y-CqE4P ring was more electrophilic and a weakerT-electron
donor than the T\-C~H~ ring
[I033.
R
0
P
%R
mN3
7.12
7.
(iii)
General Chemistry
Caulton has reviewed the coordination chemistry of the manganese and rhenium fragments (I-C~H~)M(CO)~ [104]. Reaction of the dicarbonylmanganese complexes (7.13; R = H, Ne) with the stereochemically rigid diisocyanides (L-L) 1,3- and 1,4-
7.13
References
p. 128
7.14
34 diisocyanobenzene, !I,&'-diisocyenobiphenyl and 1+,4'-diisocyanodiphenylmethane afforded mixtures of oligomers of the type [(RC;.I!Li~nl;O)n(L-L)n_~l ]"'[PF6-], [IOS]. R
1 3
I~;ethylcymantreneunderwent addition with liittig reagents, 2 ? P=IJHR-, where K 1 = ICe, R ' = 1: = Le , to form A and 2' zz j$:t, R
the products
(7.14;
i?' =
Pie,
$
=
3;
2'
=
L'rt, A2
'Treatment of the chloromethyl derivative
=
he)
(7.15)
[106].
with
:laOCH2CSXi gave the dicarbonylmanganese complex (7.16).
A
similar
reaction ~2s used to prepare the cymantrenyl derivative (7.17) [107].
The Priedel-Crafts reaction on t-butyl derivatives of cymantrene has produced the ester
phe
(7.'?8).
structure
of
tine
CorniJlex
(7.16)
was confirmed by X-ray analysis bos]. Several cymantrenylthioketone complexes [7.19; H = Pie, i-‘h, ave been prepared by &IL = ;J(CO)s; 8 = Ph, i,L z im(C0)2(Tj-CsHS h
13
CH2Cl
;r 0
CH2\
9
/CR2
Mn (CO),
7.15
Mn Gil (CO)2
CH
7.16
Me
7.17
7.16
35
Mn
treating the cymantrenylthioketone with the appropriate metal carbonyl [109]. The thermally unstable nitrosyl complex (7.20; L = CO) underwent coupling in the presence of zinc amalgam to give the dimer [(~-C$i5)Nn(CC)i:O]*while with phosphines the derivatives [7.2O; L = PPhg, P(OPh)3, P(C H ) ] were obtained. By contrast, attack 6 11 3 with hard Lewis bases such as pyridine, dimethyl sulphoxide and acetone caused decomposition with the binuclear complex (7.21; X = I) as the only nitrosyl containing product. Other members of the same series (7.21; X = Br, Cl, GO*, Me, Et) were obtained by nucleophilic attack of X- on the cation Treatment of formylcymantrene with chloroform in the presence for example triethylbenzylI- -l ammonium chloride , produced w-cymantrenylglycolic acid IlllJ* of water and a phase transfer catalyst,
Mn NO.1.L
7.21
7.20
References
p.128
36
(CH,)n$Me3C1-
9-
SiHNeR'
0
Mn
(COJ3
7.23
7.22
SiMe-C
JCH2
!I
\R2
Q 0
Q
SiMe-
in
ml
(co)3
(co)3
The cymantrenylammonium been
prepared
with
trimothylamine.
surfactants
by treatment
was
hydrosilylation
investigated
have
salts
as cationic
of Speier's (7.24
catalyst
in yields
to Live
R1 = he,
and 7.25;
a mixture
Ph;
of lb-2250 and &-59yA
[113]. (7.26
of the corresponding
accompanied
7)
chlorides
R1 = Pie, Ph) were effective in the 2 where R = CLie20R, I-‘nyuroxy-
products
The benzylpyrazoles
reactions
mxonium
5,
alkyl
HC5CH2,
R2 = Ci+ie20H,I-hydroxycyclohexyl) respectively
n = 3,
[112].
of acetylenes
of the two isomeric
of these
(7.23;
in the presence
cyclohexyl,
(7.22;
chlorides
of the corresponding
The use
Cymantrenylsilanes
reaction
CH=CHR2
0
proceeded
and 7.27) have pyrazolines
via oxidation
by simultaneous
with
been prepared
of the pyrazoline
reduction
by
benzaldehyde.
I'hese
to ?yraZole
of the benzaldehyde
[II&].
37
I2
CH Ph 12
CH Ph
Mn (CO)3
7.26
7.27
FQ 00
BF -
4
ti
M
(W2PPh3
L
CO.NO.PPh
7.28
7.29
0 0
BFk-
Re
CO.NO.1
7.30
References
p. 128
7.31
3
38 Treatment of the q5 -indenyl complexes (7.28; hi = Mn, Re) with gave the corresponding salts (7.29; 15 = nn, tie), The indenyl ligand was removed from the complex (7.29; Pi = Nn) by
NO 3F 2
4
treatment with KX, where X = BP, I, CZJ, to give bin(LO)2PPh3X. In a similar reaction the treatment of the cation (7.30) with
potassium iodide or iodine produced the complex (7.31)
[IIS].
The triphenylgermanyl and triphenylsilyl substituted anions (7.32; M = Si, Ge) have been alkylated with methyl iodide and
Q 0
Mn-.
“I
Ph 1 3
“co
co
Ph3M CO
R
7.33
7.32
benzyl bromide to give the dicarbonylmanganese complexes (7.33; M = Si,Ge, R = Me, CH2Ph).
The 'H !WR spectra of the benzyl
derivatives showed a sharp singlet for the CH2 groups which indicated that carbonyls were arranged diagonally to one another assuming that the molecule had a square pyramidal geometry
CO
H I 2
Fe
7.34
7.35
[II61.
39
The metallocene analogues of phenylalanine, D,L-P-cymantrenyl alanine (7.34) and D,L-p-tricarbonyl(r\-cyclobutadienylalanine)iron (7.35) have been prepared Cais and Tirosh
[117].
have reported the preparation of the
manganese labelled phenobarbitone haptens (7.36 and 7.37) via (cymantrenylsulphonyl)acetic acid and 2-(cymantrenylsulphonyl)ethylamine respectively.
Atomic absorption spectroscopy was used
to determine manganese concentrations in buffered solutions of the metallohapten containing immunoassay concentrations of antiThe results indicated 4;" feasibility -1 range of quantitative detection of manganese in the 10 g ml
phenobarbitone antisera. [IIS].
Et
Ph 0
0
0
S02CH2CoNH(CH&NYNH
SOz(CH2)ZNHCOCH2NYNH 0
0
Mn
Mn
w3
(W3
7.37
7.36
-Cyclopentadienyl-, r\5-indenyl-and r\5-fluorenyl-tricarbonylmanganese have been shown to exhibit approximately the ssme reactivity towards photosubstitution of a carbonyl group by triphenylphosphine
[119].
Cymantrene and methylcymantrene have been subjected to Cymantrene gave the
photolysis in glassy matrices at 77 OK.
species (r\-C5HS)Mn(C0)2, (r\-C5HS)Mn(CO) and, when ethers were present, (y-C5HS)Mn(C0)2(ether) and (s\-C5HS)Mn(CO)(ether)2. Methylcymantrene gave similar species although both substrates Rather underwent slower photolysis than the d6 hexacarbonyls. similar
behaviour on photolysis was observed for the ComPlexes
(r\-C6H6)Cr(CO)3, (~-c~H~)M~(co)~cs, [~\-c~(cF~)~S(C~F~)]M~(CC)~ References p. 128
40 and (v-CsH5)Fe(C0)21
[IZO].
The photochemically generated THF complex (7.38)
has been
attacked by ally1 alcohol and the product subjected to prototrophic elimination of water with HPFo-Ac20 to form the cationic (q-allyl)manganese complex (7.39). were formed in the same way
Several methJilated derivatives
[IZI].
9 0
Mn
(co)~THF
7.38
7.39
Irradiation of cymantrene with (q-C5H5CrSCMe3)2S produced the complex (7.40) and the structure of this molecule was determined by X-ray analysis [122]. Irradiation of methylcymantrene with diphenylsilane gave the dicarbonylmanganese complex (7.41;
X = H).
Treatment of this
CMe CMe3 I
3l
I (CO),Ph
Pin(CO)2H
b I
0
7.40
7.41
SiXPh2
41 complex with [Ph3C]BF4 in dichloromethane or with carbon tetrachloride in the presence of phosphorus(V) chloride gave the halogen derivatives (7.41;
X = F and Cl) respectively.
Reaction
of the latter complexes with carbon monoxide under pressure led to methylcymantrene silane
and the corresponding monohalogenodiphenyl-
[123].
Reaction of lithiocymantrene with the quinone (7.42) produced the alcohol (7.43)
which was reduced with zinc-hydrochloric acid
to give the corresponding phenol (7.44).
Oxidation of this
phenol gave the tricarbonylmanganese radical complex (7.45).
A
similar series of reactions was performed starting from lithiobenchrotrene
[124]. Lithiation of (dimethylamino)methylcymantrene using n-butyl-
lithium at -70 'C gave the lithio intermediate (7.46;
7.42
7.44
References P. 128
7.43
7.45
X = Li)
42
and this was treated with deuterium oxide, dimethyl~orm~ide
and
chlorodiphenylphosphine
to form the 1,2-disubstituted cymantreaes Hydroxymcthylcymantrene X = D, CHO, PPh2) respectively.
(7.46;
underwent similar metallation and attack by electrophilic reagents to form 2-substituted derivatives while diphenylphosphinocymantrene
gave
1,3-disubstituted
products under similar conditions.
The orientatjon of the reactions was confirmed by chemical methods spectroscopy and by IH and 13C lYI"IR
[125].
Mn 7.47
7.46
The cymantrenylchLoroacety1
complex
(~-C~~~.GCCH,C1)~(COf3,
has been treated with the sodio complexes, NaM(CO)n(?-CSHS), where M = Fe, W, No and n = 2, 3 to form the ci-motallated ketones f-7.47;
H = Fe,
w, Mo,
~%thy~c~a~t~ene
n = 2,
3)
[?263.
(7.48) u~der~~e~t ligand exchange with methyl
substituted Senzenes in the presence of aluminium Chloride to forum
7.48
7.49
43
the cations (7.49; arene = benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, durene, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene) [127, 1281. UV irradiation of tricarbonyl(r\-pyrrolyl)manganese with the metal carbonyls complexes (7.50)
M(CO)5
(coj3
7.50
Metallation of (T-pyrrolyl)manganesetricarbonyl (7.51) with n-butyllithium and subsequent quenching with D20 gave a trinucl,ear complex (7.52) formed by attack of the metallating agent at a carbonyl group.
Deuterium was not taken up into the product
(7.52), the molecular structure of which was determined by X-ray crystallography [I301. Picric acid attacked (y-pyrrolyl)manganesetricarbonyl
7.52
7.51
References
p. 128
(7.51)
44
NO
\2
7.54
7.53
to form which
a binuclear
has been
complex
determined
The kinetics
(7.53) the molecular
by X-ray
of nucleophilic
(7-b enzene)tricarbonylmanganese neutral
species
overall
rate
crystallography attack
cation,
to that for anion
addition
>CW-
dimethylforrnamide
at -10 'C to give of this product lithium
aluminium
on the
to give the corresponding investigated.
was unusual
to free carbeniwn
ions
b32]. has been treated
in THF at -70 'C and then ammonium
the formal
(7.55) were hydride
derivative described
(7.55;).
Several
includintJ reduction
to the corresponding
The
and it was similar
Tricarbonyl(q\-lithiocyclopentadlenyl)rhenium with
of
[131).
by anions
(7.54; X = X3, OH, CR), were
trend I??- >>OH-
structure
methanol
chloride reactions with
derivative
[133].
Q
CHO
0
Re
Re
co)y
w3
7.55
7,56
PPh 3’ Cl
7.37
45 Chlorination of the rhenium complex (7.56) with chlorine or thionyl chloride produced the salt (7.57).
Similar reactions
were carried out with tricarbonyl(\-cyclopentadienyl)rhenium The dicarbonylhydridorhenium complexes [7.58; X = SiPh3, Si(CH2Ph)3, SiPh,H] h ave been prepared by ultraviolet irradiation of
tricarbonyl(?-cyclopentadienyl)rhenium
silane.
The hydrides
with the appropriate
(7.58; X = SiPh3, GeC13, GeBr3, SnC13) were
obtained by protonation of the corresponding anions (7.59)
Re-H
[135].
Re
(CN2X
(co)2x
7.58
7.59
The hydrolysis and methanolysis of the manganese and rhenium complexes [7.60; R = H
Me Ph., L1L2 = (CO)2, (co)(Pst3), (CO) (PPh3), Ph2PCH2CH2;Ph2'] and (7.61) have been studied.
The
carbenium ions generated in these reactions were stabilized better by phosphine ligands than by the carbonyl group on manganese. The stabilizing abilities of manganese and rhenium were the same [136].
7.60
References
p. 128
7.61
46
.
(iv) Applications 3N-Methylcymantrene,
orally administered to rats, was efficiently absorbed, metabolized and excreted in the urine as the alcohol (7.62; R = CH2OH) and as the carboxylic acid (7.62; R = COZH).
In vitro, the same complex was metabolized by rat liver microsomes by a cytochrome P 4SO-dependent process [137].
Mn (W3
7.62
The toxicity of methylcymantrene in rats has been investigated.
The LDSO dose was 50 mg/kg for oral administration and
23 mg/kg for i.p. administration. Histological examination of rats treated with methylcymantrene revealed pathological changes in the lungs, liver and kidney.
Phenobarbital pretreatment protected rats from the lethal effects of 2.5 times the LD dose Polymer-bounddinitrogen complexes were prepared by treating vinylpyrrolidinone-tricarbonyl(~-vinylmethylcyclopentadienyl)manganese-styrene atmospheres).
copolymers with nitrogen under pressure (3
These dinitrogen complexes were more stable than
the corresponding monomer model dicarbonyldinitrogen
(?-methyl-
cyclopentadienyl)manganese
[I39-J No significant chain transfer was observed on polymerization
of styrene in the presence of cymantrene or poly(?'-vinylcylopentadienyl)tricarbonylmanganese [140]. Cymantrene has been incorporated with advantage into a fire extinguishing composition [141]. Extensive fleet trials of methylcymantrene as a gasoline antiknock additive have been subjected to statistical analysis in order to provide mathematical models for the effect of the
47
additive.
Hydrocarbon emissions increased linearly with additive
concentration while catalyst converter efficiency was increased in the presence of methylcymantrene
[142].
Methylcymantrene has been determined at ng/m3 concentrations in air. The sample was trapped in a small segment of a gas chromatography column and measured by gas chromatography using an electrothermal atomic absorption spectrometry detector.
The
limit of detection was found to be 0.05 ng/m3 [143]. 8.
Polynuclear (n-C$15)Mn(CO)3 Complexes
The THF derivative of cymantrene, (1-C5HS)~(C0)2(OC4Hs) combined with COS and COSe to form the binuclear complexes (8.1; X =
S,
Se).
An X-ray crystallographic investigation of the
sulphur compound (8.1;
X = S)
confirmed that the molecule was
centrosymmetric with a planar MI-I-S-S-WIunit
Mn-X
c-s-Mn
-x-Mn
8.2
8.1
The
I3 C
[IQ.].
IW3 spectra of cymantrenylphenylthioketone
binuclear complex (8.2)
and the The
have been recorded and interpreted.
structure of the complex (8.2)
was determined by X-ray analysis
[I45 J. The electronic structure of the cluster complex/4-CH2-[(yCgH5)"n(CO)& h as been investigated by vapour-phase photoelectron spectroscopy and by quantum mechanical calculations. The molecular orbitals used in formation of the cyclic Mn-CH2-Mn bridge were discussed [146, 1471. The crystal and molecular structure of the same complex has been determined by X-ray The molecule contains two trans-(l-C5HS)ph(CC)2
crystallography. References p. 128
48
r~roups joined by a bri:Qing methglene g;roup. rho maii~;acesemanganese interatomic distance was L.799 a [l&ii]* Tile Hc I r>iiotoelcctrons~sectrum ir; the ioniza.tion enorgy complex {o._3) range below 11 ev has been recorded for tile tzidjg3d
and cornpared with the spectra of methylcymantrene and It was concluded tilnt ttx?liul-Pin bond (~-C4"'"4"e)Mn(C0)2(~-C;?IIIC~, in (P.3) was an important factor i:l the stability of this compound [?tq. The irradiation of cymantsene with HECC02Pie in tetPahYdrofuran gave the dicarbonylmanganese derivatives (8.4 and ij.5) as the major products. Treatment of the manganese complex (8.4) with hydrogen chloride produced the corresponding q-olefin derivative (i-,.6)[1503.
(2 0
Q III
//JCH2\w,
Nn
0
c co
Pin
Me
2
IQl---
OX),
(CO)*
8.h.
6.3
Q 0
Pin-
(CO)2
CECl
8.6
CH
49
ma2 Mn=Ge=
Mn
a.7
8.8
Treatment of the hydride K[(r\-WeC5H4)Pii(CO)2GeH3]with acetic acid gave the trinuclear complex (8.7) which has been characterized by X-ray crystallography. The molecule is centrosymmetric and contains a linear Nn=Ge=Nn moiety with Mn-Ge double bonds. Treatment of the same hydride with mercury(I1) gave the trimanganese germanium complex (8.8) which contained a I??-Ge double bond in addition to a triangular Mn2Ge ring [ISI]. Reaction of methylcymantrene with GeH3K gave the potassium salt (8.9) which when treated with germanium tetrachloride produced the neutral complex (8. IO) [152].
Treatment of the salt
(8.9) with mercury(I1) chloride gave the tetramercury derivative (8.11) [153].
Q 0
Mn
(C0)2GeH3
8.9
References
p. 128
8.10
8.11
9.
Carbene and Carbyne (I\-C~~I~)M~(CO)~
Complexes
The methylpropiolate complex (9.1) was attacked by organolithium compounds, RLi, where R = Me, But, Ph, to give the carbene complex (9.2) in 50% yield [154]. Treatment of the methylcymantrene complex (9.3) with Me03SF gave the phosphorylid-carbene complex (9.4; R = H) and then the salt (9.5) in the presence of an excess of Me0 SF. The product 3 (9.5) was attacked by Me3P=CH2 to give the phosphorylid-carbene complex (9.4; R = Me) [li;S]. The reaction of dicarbonyl(q-methylcyclopentadienyl)-
C02Me I
Q 0
&-_
Mn-
--
(W2
(W2
9.1
9.2
\
C02Me
51
I
Q (0z$L?Me3 0
PMe + 4
OM6
9*3
9.4
FSO 3
9.5 (dior~~y~allenylidena)mang~esa
compounds with t-b~tyll~thi~
followed by protonation or methylation gave the vinylidene complexes (9.6; R = H, Me; and 9.7).
!!%a structure of the complex
(9.8) was determined by X-ray analysis lj%J* The carbene complex (9.9), obtained by treatment of Ph2C=M(CO)S with (y-CsH 5 )Mn(CO)$!RF, underwent photolysis to form tetraphenylethylene, diphenylmethane and 1,1,2,2-tetraphenylethane [1573* Treatment of the manganese complexes (9.10; R = C=CHCO2Me, T-CHZCCO~M~, C=C=CPh2) with nonacarbanyldiiron gave the corresponding tetracarbonyliron derivatives (9.11; R' = M, R2 = CO2Me; R' = CO Me R2 = B; R'R* = CPh2) [~583. 2 9 The electronic structures and bonding capabilities of the
References pa 128
101
P
tX
0
Fe
PF6-
PF6-
b 0
14.19
14.18
CN /
Fe
t?f+ 0
I
0 0
14.21
14.20
Q 0
Fe
+
Q
COR2
0
1
b0
J
14.22
References
p. 128
14.23
+
102 Reduction of the (T-benzene)(n,-cyclopentadienyl)iron cation (14.24; n = 1) with sodium amalgam gave the neutral complex (14.24; n = 0) in addition to the (v-cyclohexadienyl)iron complex (14.25) [2723.
a
Ph
P 0
n-t
;*-‘ 1 ‘._.
Ph
Fe
Fe
6
6 0
0
14.24
14.25
Electrochemical reduction
of the
( -arene)iron
cation
(14.26) gave successively the neutral rzdical (14.27) and the anion (14.28) which was attacked by iodobenzene and methyl iodide to
form
the (y-cyclohexadienyl)iron complexes (14.29; A = Ph, Pie).
273. , F 3 The electrochemical reduction of (7 -arene)(q'-cyclopentadienyl)iron cations in basic media has been studied. One-
Several related reactions were reported
electron reversible electroreduction occurred to give the corresponding radicals, that is the neutral 19 electron d7 complexes (?6-arene)(\6-C5H3)Fe(I). The behaviour of the radicals depended on the nature and the number of the substituents on the rings and also on the medium.
With all the radicals catalytic
reduction of the medium occurred together with radical dimerization or decomposition liberating Fe(O) or Fe(II) [274]. The (T-chlorobenzene)iron cation (14.30) has been reduced with sodium amalgam at -10 'C to give neutral (n,-chlorobenzene)(r\-cyclopentadienyl)iron which dimerized in air and in aqueous sodium borohydride
[275].
Hydrogen atom abstraction with oxygen from the neutral (T'-hexamethylbenzene)iron complex (14.31) gave the (n,5-benzyl)iron complex (14.32) which has been characterized by X-ray crystallography.
The exocyclic methylene is bent away from the
103
14.27
14.26
Q
Q
I-.
a’
R
0
‘._M
Fil
Fe
+ P 1 14.29
Cl
0
Fe
6 0
14.30
References p. 128
L
14.28
P 0
Fe
6
6 0
iron atom
and out of t:ie plane
(14.32) acted
complex metallic
t,
halides,
0
of the six-membered
as a nucleophile Ph2PC1,
PhCOCl,
Y-
14.33
14.32
14.31
CH2X
Fe
Fe
0
+
to organic
he3SiC1,
ring.
The
and organo-
hn(CO)jBr,
C H )Fe(CO)i2C1, to form the (l-arene)iron salts ['i&.33; ('i- 5 5 X = GOPh, PPh2, SiiGe?, r?ln(CO);, Fe(CO)~(~5,-C~KS), Y = Cl, Rr] , [2763. The peralkyl
$
= E; *I
reduction
of the corresponding
(;4.34) were
characterized
by spectroscopic (q-arene)iron
R1
(?&.jlb; RI
(t\-arene)iron complexes
= R'’ = Ne) have been obtained
1
to
compounds
complexes
of Fe(I)
The methylsted 5)
dimerize
R1 Men
M Fe
14.34
23 ,
The green
techniques.
(14.35; n =
Me,
amalgam
as d 7 19-electron
and magnetic
complexes
cations.
=
by sodium
14.35
thermally
105
at -20 'C through the arene ring.
The complexes (14.34
and
14.35) Were effective redox catalysts [277].
reaction with oxygen to give the corresponding q-cyclohexadlenyl complexes with doubly bonded exocyclic methylene groups.
FOP
example, (+$I$ Fe(l-C61vie6) produced the ?-cyclohexadienyl complex (lic.36). This latter complex underwent nucleophilic substitution with, for example, CB I, PhCOCl, Ke3SiC1, Ph2PC1 (~-CSHS)Fe(CO)2C1, (i~-Cg"~)No(C0)~?,I%A(CO)~B~, CP(GO)~ and nucleophilic addition with, f'or example, CO2, CS2 and
Q
,/--Qi 0
Fe
I
‘._.
CH2
14.36
15.
(~I-C&~RU
and (II-C~J&&~
Treatment of the ruthenium complexes (15.1, cyclopentadiene gave ruthenocene
Q 0
Ru
(PPh3)2X
IS.1
References ps128
[2.793.
X =
H, Cl) with
106 Ruthenocene
underwent
+0.68 v, 100 mv s
-1
, on voltammetry
AlCl3:n-butylpyridinium
chloride
electrodes.
In acidic
was
by a multistep
oxidized
composition The
have
melts
of the melt
corresponding
shifts
and compared
ferrocenophanes
The reduction borohydride
acid produced
Irradiation
on the nature
In addition
ruthenocenophanes
[3]ruthenocenophan-l-one
the values
with
chloride,
substitution
[202].
with
the product Carbon
of ruthenocene,
and dichloromethane
the formation
sodium borontrif'luoride
in ethanol-polychloromethane
ethoxycarbonylation
containing
for the
of the polychloromethane.
to substitution,
with
cyclopentenes
ruthenocene 3 sensitive to the
I,1 I-diethylruthenocene
depending
formylation
ratio carbon
of AlCl was
several
and
of aluminium
led to photochemical
oxidation
for
with
of ruthenocene
caused
which
Lp,2 =
[Zol].
solutions
chloride
vitreous
of l,l'-diacetylruthenocene
in the presence
or sulphuric
using
an excess
sequence
[k]ruthenocenophan-Z-one
been measured
caused
in an 0.8:1 molar
melt
with
oxidation,
[Zoo].
I3 C NKR chemical
including
an irreversible
carbon of
chloro
caused
tetra-
ChlOrOfOrm
ethoxymethglation.
tetrachloride
favoured
[(~-C5H5)2R~]tR~C14and trichloromethyl
and substituents
[283]. Perrocenylruthenocene coupling
in the melt.
Mass
lower metal-ligand
[?84].
Q-9 0
(15.2) has
of iodoruthenocene
0
with
spectrometry bond
strength
been
a large
obtained
excess
of the complex
by Ullmann
of iodoferrocene (I:>._')indicated
for iron than for ruthenium
107 The [3.3](1,1~)-
and (S,S](l,l')-ruthenocenophanes and the
fefrocenoruthenocenophane homologues have been prepared. For example, the reaction Of ?,I'-ruthenocenedicarboxaldehyde with l,l'-diacetylruthenocene in ethanol in the presence ethoxide gave the ruthenocenophane
(15.3)
of
in good yield
Vinylruthenocene has been homopolymerized and
sodium
[285].
solution
copolymerized with methylacrylate,
styrene and vinylpyrrolidine in the presence of azobisisobutyronitrile as catalyst. The
Pollers 3.13
x
were benzene soluble with molecular weights of 103-1 .3
3.1-13.2. analysis
x 705 and molecular weight distributions of
The polymers were investigated by thermogravimetric [286].
Polyruthenocenylene oligomers have been prepared by the coupling of the l,lf-dilithioruthenocene-1,2-bis(dimethylamino~ethane complex in the presence of copper
chloride [287].
Hydroxyfase activity in rats and mice has been studied using 103 Ru-ruthenocene. Greater hydroxylation was observed in male than in female animals and after pretreatment with barbiturates.
The distribution of 103 Ru in lung and kidney
after administration of 103 Ru-ruthenocene was affected by barbit;;ate pretreatment
[28S).
Ru-Labelled ruthenocenecarbaldehyde was treated with glucosamine, galaotosamine and mannosamine to give the oorresponding Schiff bases which were reduced at the C=N bond and the aldehyde
14C-Labelled glucosamine was also condensed
group.
with ruthenocenecarbaldehyde
to give the corresponding labelled
amino sugar derivative of ruthenocene
[289].
The metabolism of ruthenocene derivatives ofamino-sugars labelled with lo3Ru has been investigated. The derivatives were concentrated in the kidney and liver of tumour-bearing mice and excretion was rapid as the unmetabolized amino-sugar. stability
of
results
[290].
16.
The
the ruthenocene group was demonstrated by these
h-CpSNOh~CS~;~
Dicarbonyl(n,-cyclopentadienyl)cobalt combined with l,2(16.1) to form 1,2,4-triphenyl-3(~-~henylethynylphenyl)biphenylene as the major product together with the (y-cyclobutadiene)cobalt and (q-cyclopentadienone)cobalt
bis(phenylethynyl)benzene
Referencesp. 128
108
*
'Ph
I
16.1
‘Ph
16.2
complexes
(16.2 and 16.3)
(n,-cYclobutadierle)cobalt X-ray
crystallography,
respectively. complex
The related
(y-cyclopentadienyl)rhodium
and
The structure
(16.2) has reaction
the ligand
of the
been confirmed
by
of dicarbonyl(16.1) was reported
[291].
Coupling
;
constants,
J(C1-C?)
and J(C2-H)
the former trigonal
been
obtained
(v, -dlpnenylmethoxycyclobutadiene)-
C IJDiRsnectroscopy for by tricarbonylcobaltium hexafluorophosphate.
was
have
4 -. .
13
was
the lowest
carbon
atoms.
in accordance
with
reported
The value values
The value
for l-bond
for the latter
previously
the separation
of closely
related
for
between
was high
reported
c Y clobutadier.e)tricerbonyliron complexes '"\High performance liquid chromatography
obtained
coupling
and
for substituted
[292]. has been used
(T-cyclobutadiene)-
for
109
16.4
16.5
(I-cyclopentadienyl)cobalt complexes such as diastereoisomers and structural isomers. Reversed phase chromatography has been used with octadecylsilyl-modified silica as a stationary phase and
pOLa??
mobile phases saturated with argon.
Thus the diastereoisomers (16.4 and 16.5) which were inseparable by 4LC Were conveniently separated using acetonitrile/water (9/l) [293, 2941. Cyclic voltammetry and polarography have been used to show that (y-cyclobutadiene)(\-cyclopentadienyl)cobalt underwent reversible electrochemical oxidation [2953. The mechanism of formation of \4-cyclobutadiene-metal compounds, by the interaction of transition metal complexes with alkynes, has been investigated. and 16.8)
were
Compounds of the type (16.6
subject to flash vacuum pyrolysis and extensive
eouilibration between these two compounds was observed.
From
the results it was concluded that the cobalt complexes (16.6 and 16.8) reversibly isomerized through the intermediate (16.7) by single alkyne rotation [296]. Gas phase rearrangement of the (y-cyclobutadiene)cobalt complex (16.9; R1 = Rz = SiMe3, R 3= R4_- CECH) gave the product (16.9;
R1
=
R*
=
C=_CSiPiej,
R3 = R4 = H).
It was considered that
the corresponding rearrangement of the complex (16.9; R' = R2 = H, R3 = R4 = CECH) could involve the intermediate (16.10) [297]. The treatment of the t\-tetraphenyl-cobalt complex (16.11) with lithium tetrachloropalladate(I1) in the presence of sodium acetate gave the ortho-palladated compound (16.12).
The
reactions of this latter compound with carbon monoxide and
References
p. 128
110
H SiMe
SiMe co
3
3
3
16.7
16.6
%
16.8
R1
R4
16.9
16.10
111
Ph
Ph
Ph
Ph
Ph
Ph
NMe2 I Td-
Cl
2 16.11
16.12
olef'ins were examined
[298].
A complete product analysis for the reaction of dicarbonyl(y-cyclopentadienyl)cobalt with 1,6-bis(trimethylsilyl)-l,~hexadiyne has been carried out.
Eighteen metal complexes were characterized and these were formed by oligomerization of the diyne to give mixed cyclobutadienes, cyclopentadienones and
biscarbgne clusters [299]. (q4-Cyclooctadiene)- and (q4-cyclooctatetraene)(n\-cyclopentadienyl)cobalt have been investigated electrochemically.
For both the complexes the l,S-bonded isomer was
thermodynamically more stable in the neutral compounds and less stable in the anions on reduction [300]. 17.
Cobaltocene has been obtained in 52% yield by heating cyclopentadiene with cobalt(I1) ethoxide and diethylamine [301-j* In a similar preparation cobalt(I1) ethoxide was treated with cyclopentadiene in the presence of sodium cyclopentadienide [302]. Reaction of sodium cyclopentadienide with ethyl formate, methyl acetate or methylcarbonate afforded the substituted sodium cyclopentadienide derivatives (17.1; R = H, Me and OMe) respectively. Reaction of the organosodium reagents (17.1; R = Me, OMe) with cobalt(II) chloride or nickel(I1) bromide produced the corresponding cobaltocene and nickelocene
References
p. 128
112
Q
i Q
C=CH2
COR
0
COR
0
co
(CO$ COR
17.2
17.1
17.3
I
R
0
CHOCOCH=CH2
Q CO
17.4
(17.2;
derivatives
M
cyclopentadienide as precursors monomers
= Co,
Ni; R = Me, OMe).
derivatives
(17.1;
in the preparation
(17.3
17.i~)
and
The reaction
[303,
of the new organometallic
3041.
of dicarbonyl(l-cyclopentadienyl)cobalt
cyclohepta-1,3-diene
and cyclohepta-1,3,S-triene
corresponding
complexes
abstraction gave
cobalt from
the stable
(17.6) with
cation
(17.7).
(17.9).
and 17.6).
Proton
produced
gave
Hydride
abstraction
the anion
gave
Hydride
the
with the
of complex from
(17.8)
of dicarbonyl(l-cyclopentadienyl)cobalt
or 1,3-cyclohexadiene complex
(17.5
(17.5) or protonation
complex
n-butyllithium
Reaction
The sodium
R = H, Pie, OIGe) were used
[33;]. with
(q4-1,3-cyclohexadiene)-cobalt
abstraction
produced
(17.6)
complex
the dication
1,4-
\Q/ co
/\ / 0
6
6
17.5
17.6
113
co
0
0
:0,\. ,’
‘._-’
CO
_6 0
17.7
(17.10).
+
s1 o0
CO
6 0
17.8
Treatment of the dication (17.10) with sodium methoxide
or sodium cyclopentadienide gave double, vicinal and stereospecific (exo) addition to the benzene ring in accord with the Davies-Green-Bingos rules [306]. The photolysis of (r\-C5H5)Co(CO)2 in an aromatic solvent such as benzene or toluene afforded the corresponding (?-C5RS)Co(y-arene) and (r\-CSHS)Co(l-arene)2 complexes. The benzene complex (~-C5HS)C~(~-C6H6) combined with Z-butyne to give the hexamethylbenzene derivative (y-C5HS)Co(y-C6Me6) but failed to catalyse the formation of free hexamethylbenzene from an excess of 2-butyne [307]. Decamethylcobaltocene has been prepared from (MeOCH2CH20Me)CoBr2 and lithium pentamethylcyclopentadienyl and it readily underwent reaction with the electrophiles RX (MeI, Phi, ClCR2I, References
p. 128
114
(=j
p-
2+
co
co
6
t0
0
~
.
17.10
17.9
MeOCH2C1, MeCKClI) to give the products of oxidative addition (17.11).
This reaction with the chl.oroiodoalkanes gave the
corresponding exo-chloroalkyl derivatives (17.11) and these compounds underwent solvolytic ring expansion to form the n\-cyclohexadienyl cations (17.12; R = H, Me) [3081. The y4-cyclopentadiene compounds (17.13; X1 = Ph, pie;
R2 = Me) rearranged the corresponding Treatment
when heated cobalt
of these
or triphenylmethyl cobaltocenium
salts
in methylcyclohexane
complexes
complexes
with
to give
(17.13; R1 = H, R' = Ph, Me). ammonium
hexaf'luorophosphate
hexafluorophosphate
produced
(17.14; R = Ph, Ne)
the corresponding
[309].
Several reactions of' di(q-cyclopentadienyl)dicobalttetraiodide have been reported including reduction with sodium amalgam to form cobaltocene
c310 I+
0 *
+
0
.-: -3 *
CO
** -. .
co
R
l
'L
R
17.11
17.12
115
R
0 0 CO
0
t\
17.13
17.14
Thallium-cyclopentadienide
and -methylcyclopentadienide
treated with rhodium(II1) chloride to give the rhodocenium cations (17.15; R1 = R2 =H; R1 = H, R2 = Me; R1 = R2 = Me).
Were
Oxidation of the latter two complexes with potassium permangana te produced the corresponding acids which were converted to the acid chlorides (17.15; R1 = H, R2 = COCl; R1 = R2 = COCl). Treatment of the acid chlorides with sodium azide gave the amides (17.15; R' = H, R2 = CONH2; R' = R2 = CONH2) [311]. The reaction of tetraacetatodirhodium with pentakis(methoxycarbonyl)cyclopentadiene unexpectedly produced the rhodocenium salt (17.16) where two of the C02Me groups in each The structure of the salt (17.16) was determined by X-ray analysis. Both the CS-rings were ring had been replaced by H.
-bonded and they were fully staggered which allowed the bulky
Q b
1k
R'
C02Me
Me02C
0
Rh
0
Rh
R2
C02Me
Me02C
Co2Me 17.15 References
p. 128
17.16
116 C02Ne
groups
to intermesh
Addition
of the ?-diborabenzene
trifluoroacetic sandwich
electron
corresponding
complex
acid at -80 '6 nroduced
complex
valence
[312].
("7.18; n = 2) in high complex
singly
(17.17)
yield.
.Phis thirty
was electrochemically 31 electron
charged
to
the tri!jle-decided
reduced
cation
to the
(17.18; n = I)
[313]. n+
7% -Q0
0
Rh
Rh
Rh 17.17
0
17.18
+ The 'E and cobaltocenium preted.
C IPIR svectra
spectra It was
density
over
central
metal
(17.19)
yield
were
compared
concluded
the metallocene atom
Electrochemical
cation
of a series
hexafluorophosphates
The
analogues.
13
in acid (17.20)
that
of s-methyl-
have
been
recorded
with
those
of the ferrocene
the distribution
molecules
and inter-
of electron
was dominated
by the
[314-J. reduction
solution isolated
gave
of the cobaltocenium
cation
the hydroxymethylcobaltocenium
as the tetraphenylborate
salt in 602
[315]. Attack
lithium cobalt
gave
of the cobaltocenium the corresponding
complexes
(17.21; R = Me,
hydride
abstractinn
to give
the substituted
respectively
cation
[316].
with
with methyl-
exo-substituted Ph) which
triphenylmethylium cobaltocenium
or phenyl-
(v-cyclopentadiene)-
underwent
e-
tetrafluoroborate
cations
(17.~2; R = Pie, Ph)
117
Q
-I-
CH20H
Co2Et
0
CO
17.19
I
17.20
Cobaltocenium halides were prepared by oxidizing cobaltocene with 0.01-0.03 M bromine or iodine in a hydrocarbon-tetrahydrof'uran solvent mixture at O-5 ' in an inert atmosphere
[317].
R H +
Q
R
0
4
CO
6 0
6
17.21
0
17.22
The intercalation compound Zr(HP0 ) 4 l.5(po4)o.s [V5H5)2Colo.~ has been obtained by treatment of cobaltocene r*ith ZI?(HPO~)~.H~O [318]. Nesmeyanov and co-workers have reported a method for improving the strength and yield of l,l'-diacetylcobaltocenium hexafluorophosphate copolymers
[319]. Mercaptoorganosiloxanes were used, with cobaltocene as catalyst, to prepare one-package sealing compositions which were
stable in the absence of oxygen and were cured in the presence of oxygen [320].
References
p. 128
118 18.
Cobalt-carbon Cluster Compounds The cobalt-carbon cluster compounds
[i8.1; R = CH CO Ne, 2 2 CH(CO2Me)2] were formed unexpectedly by the reaction of methyl acetylenecarboxylate or di(methy1) acety lened icarboxylate with [321].
COAX
i
(co)3co-
c\/ /I
I\
coom3
co(co)3
18.1
Prolonged reaction of sodium tetracarbonylcobaltate with (ClMe2Si)2 gave the cobalt cluster compounds (18.2 and 16.3) [322].
The alkylidynecobalt nonacarbonyl complexes (18.4; X = Cl, Br, H) have been prepared in a one step process.
Cobalt(i1)
nitrate in aqueous ammonia was reduced with sodium dithionite under an atmosphere of carbon monoxide at room pressure in the presence of a benzene solution of the halocarbon containing cetyltrimethylammoniutn bromide as the phase transfer catalyst.
OSiMe2SiMe2Co(CO)
4
c\co(co, / \
SiMe2 \Co(CO)
3
(co)3co
/I -Co(COj3
18.2
(CO)3GO-
/I
3
WI82
18.3
119
i
c\CO(Co) / / 3 I/ \I \/l I
(CO) co3
w3c
Co(CO)3
\
,L
o----co(co)3
18.5
18.8
The cobalt cluster complex was isolated from the organic layer after two hours
[323].
An unsuccessful attempt has been made to prepare alkylidynetrirhodium complexes by the reaction of Na[Rh(C0)2(PPh3)2]with The major product was RhX(CO)(PPh,)., where halocarbons. ,'L X = Cl, Br [324]. The methyl substituted cluster complex C18.5; Y = Co(CO)3] has been treated with (l-cyclopentadienyl)metal carbonyls to _ give the derivatives
[18.5;
Y
=
Mo(~-C~H~)(CO)~, W(Y-C~H~)(CO)~,
Fe(y-C5H5)C0, Ni(T-CsHS)] [325]. Treatment of the cobalt complex (18.6)
with the hydrides
R3MH (M = Si, R3 = Me3, Ph3, Me2C1, MePhCl; M = Ge, R3 = Ph3, Et?, Ph2C1, Et2C1) produced the corresponding silicon and Alcoholysis of chlorosilane germanium derivatives (18.7). H
MR
I
c~coo / I\A
I3
3
(CO)po
-co(co)3
18.6
References p. 128
18.7
120 (18.7;
derivative alkoxy with
MR3
derivatives.
= SiYIePhCl) gave These
i-Bu,Al;I or Et,OBF
hydride
alkoxy
to give
the corresponding
compounds
underwent
the corresponainr:
reaction
siiicon
or fluorideLM[32z].
The silicon-
and germanium-cluster
complexes
(16.d; M = Si,
, Ph) have been formed by metal exchan:;e with a Ce, R = ;h?;e preformed cluster or by synthesis from cicobalt octacarbonyl and
[327 3.
(q,-C5H4)(CO) 3NoSiH$Ie
i
o0
I’\corco, / 3 /I \ Co(CO)_
No-
3
(coj2 18.8
The Crystal
and molecular
nonacarbonyltricobalt have
been
determined
cluster by X-ray
complex
(16.4; X = Cl) shows
mesityl
complex
imparting
of the methylidyne(18.4; X = Cl, C6H211e3) i'he cihloro
crystallography. the expected
structure
while
the
(18.4; X = C H Me ) snows interaction between 62 3 group of the substituent and the neighbouring
the g-methyl carbonyl
structure complexes
ligands
forcing
some bridging
Ultraviolet
the latter character
photoelectron
on the co balt
calculations
into
the Co -plane 3
and
[34.
spectra
complexes
and molecular
orbital
(lil.1; H = H, Me,
Oldie,Cl,
It was suggested that the apical Br, I) have been reported. carbon was electron rich and that the T-system was sufficiently flexible concluded
to behave
as either
that
the CR group
The He(I)
photoelectron
a donor
It was
or acceptor.
was best
described
as sp 'hybridized
[329]. complexes
(16.1~;
on the basis consistent
X
of qualitative
with
s!?ectra of the cobalt
= F, Cl, Pie) have
arguments.
the interpretation
cluster
been measured
and interpreted
The results
of the cluster
were
as an electron
121
i t
co(co~3
- 1 /
(co)3co
\/
co (CO1.pPh3
18.10
18.9
sink which underwent %in-l;eraction with the substituent X [330]. The radical anion cluster complex (lS.9; X = Ph, Cl) was
obtained by electrochemical reduction and underwent nucleophilic substitution with phosphines and phosphites to f'orxn products such as the triphenylphosphine (18.10) [331]. Treatment of the tricobalt clusters c18.11; R = CONMe2, Cl, R, Ph, Ne; L = CO, PMej, P(OMe)3J with ~e*A~N~e~ gave intermediate substitution products which were highly susceptible tQ hydrolysis and derivatives (18.12) of the bidentate Ligand (Ivie2As)20 were isolated, The same compounds (28.12; L = CO) were obtained by direct substitution of the cobalt clusters (la.l?; L = co) by (Me2As)20 together with the corresponding di- and tri-substituted products
18.11
References p.128
[332].
18.12
122
18.13
18.14
The cobalt cluster compound (18.13) underwent reaction with hydrogen in aromatic solvents to give 3,3-dimethylbutene, The hydrogenation 2,2_dimethylbutane and &,4-dimethylpentanal. was inhibited by the presence of carbon monoxide [333]. Acyl- and aroyl-methyl~dynetr~cobaltnonacarbonyl cluster complexes (18.14; R = H, Me, Et, Bun, 4-Br.C&+, 4-C1.CgH4, 4-FIe.C6H4, Ph) underwent reduction with hydrogen in 4-F+& ref'luxing benzene to give sither the N-hydroxyalkylidyne complexes (18.15) or the completely reduced alkylidyne complexes (q8.16) or in some cases
a mixture
of
the
two
products.
%hen
tne reagent was trifluoroacetic acid then the alkylidyne clusters (18.16) were the exclusive products. Thermal. decarbonylation of the complexes (18.14) gave the corresponding aikyl- and arYlmethylidyne cluster complexes (18.1; R = kt, Bun, Pr', 4-Br.Cbff47
CHOHR
CH2R
I
I
18.15
18.16
123
4-cl.cbH4, 4-F.C H4, 4-Me.C6H4, Ph, 4-Me2N.C6H4, ferrocenyl, 2-pyrrolyl) [334 4 . 19.
(1\-C&@i The nickelocenes
(19.1; R = H, Et) have been prepared by reaction of the corresponding lithium cyclopentadienide with nickel chloride. 1.65 THF
0
335 .
R
*
-6-b \ /
Ni
Ni
Ni
0
R
q 19.1
19.2
Treatment of nickel(I1) chloride with bis(l-cyclopentadienyl)magnesium gave nickelocene in '72% yield
[336].
The cluster complex (T-C5HS)3Ni3(C0)2 was degraded by
heating with triphenylphosphine in THF to give a mixture of nickelocene, (PPh3)3Ni(CO) and (PPh3)2Ni(C0)2. mechanism was discussed
The reaction
[337].
The disordered phase of nickelocene at 295 OK was investigated by an X-ray diffraction study and compared with that of ferrocene.
The results showed that the evolution of the
disordered phase of nickelocene and ferrocene between 295' and _!? OK was different
[338].
The structure of bis(v-fulvalene)dinickel determined by X-ray crystallography.
(19.2) has been
The C-C bond distances
were found to show localization of multiple C-C bonding as in the neutral ligand [339]. The collison
free molecular
multiphonon dissociation (MPD)
and molecular multiphonon ionization (MPI) of nickelocene induced by the light region
References
of a tunable
dye laser in the wavelength Four reactive
3750-5200 A has been investigated.
p. 128
124 Processes
were
identified,
3.10 ev, 3-photon 3;>>2.&
and j-photon
Nultip‘hoton been
studied
resonant
have
which
recorded
resulted
decker
showed
ions produced
at 30-300
OK.
from
discussed
conformational
complex
(19.3) have
over both
The electrochemistry
melts,
a reversible
of
ratio
one-electron
ion were
ir: acidic oxidation formation
19.3
found
melts, to
atoms
the
(3PC) melt
has been
reaction
dication
ion
underwith
an d the
in chloride
ratio
nickelocecium
studied.
nicXelocene
Both nrckelocene
to be unstable
of a stable
electron
[31+33.
at 40 'C in an aluminium
AlC13:BPC,
molar
and analysed.
and -Ghe unpaired
charge-trarlsfer
>I:1
disorder
13~2 3.
been recorded
nickel
chloride
.]:I molar
El = -(;.I65 V vs. Al reference.
reversible
compounds
of tile pars-magnetic triple-
of' nickelocene
chloride-1 -bvtylpy-idiziurr
spontaneous
and non-
of dynamic
fluctuations
and '3 C WKEI spectra
distributed
solvents.
beams.
exclusive
by resonant
in terms
be‘naved like a metalloceno
n?ckelocenium
molecular
almost
has
The temperature dependence -1 ) and q.uasi-elastic
The complex
went
[jlr(j].
perdeuterated
was equally
In neutral
eV
s;:ectra (lo-200 cm
'PI, "B
sandwich
>
(10-4~~0 cm -I) of nickelocene
spectra
and the corresponding
scatterln;5 were
The
and in supersonic
and infrared
the low frequency neutron
?.6-1.9
IbiPIfor%_,
;j-photon M~i) for
[3413.
mechanisms
been
=
eV,
of nicirelocene arid frrrocene
ion detection
of bare metal
and ferrocene
molecular
3.1G-2.10
for%2
MPD
in effusive
The Raman
=
dissociation
FIaSs snectrometric generation
two-photon
TOP&J
NPI
rich
AlCl,:Ui'C, xzsiobserved
with
at E-2 = +0.91- ’ v vs.
19.4
Al.
125 The electronic spectra of nickelocene s-;ecies in the +2, +3 and +4 oxidation states have been obtained in the melts [344]. Bickelocene has been used in the preparation of the phosphine complexes [19.4; L = PPh3, Ph(n-BuJ2P, PhMe2P, Ph2MeP, (n-Bu)3P, Et3P; L2 = diphos, o-phen, bipy].
The mechanism of
substitution of nickelocene was discussed [345]. Reaction of nickelocene with the bis-ylids Ph3PCH(CH2JnCHPPh 3 (n = I-3) gave the corresponding chelate complexes (19.5). Treatment of nickelocene with the mono-ylids ethylidenetriphenylphosphorane and triphenylphosphoniumcyclopentadienylid
afforded
the cations (19.6 and 19.7) respectively [346]. Reaction of nickelocene with HP(0)(OR)2, (R = Me, fit) produced the corresponding nickelbis(phosphonate)
Q
+
Q /*=\ 0
Ph3PCH
CHPPh3
\/
Q 0
Ni
PPh3
References
p. 128
/*=\ Ph3PHC
CHPPh3 I Me
Me
19.6
19.5
2+
1
+
0
I
(CH2)n
PPh3
COmpleXeS
(?-CgHg)~Ji~['(Ol~)20]2N)which contained a six-membered NiP02Ei ring with a symmetrical O-H-O hydrogen bond [3!~7]. The reaction of nickelocene with Ru,(GO)12 gave [(rj-C~H;)Ru(Co),],,r\-C5HsNiRu3(CO)9 and'with liRu(GOjqC~2Butthe hydride F~Ru~(CO)~C~E$~ [348-j. (?'-Alkerlyl)(n;?-cyclonentadienyl)nickelcomplexes were prepared from nickelocene by treatment with alkenylmagnesium halides, isopropylmagnesium bromide and alkadienes or with methylenecycloalkanes
[349].
X3-7-Fhosphanorbornenes
have been prepared by reduction of
the corresponding phosphorus sulphides with nickelocene in the presence of propyl iodide [350]. Slocum and co-workers have demonstrated the potential of T-bonded organometallic polymers in catalyst design.
'The
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[311].
'~q-+jE&U Activated uranium prepared by the reduction of uranium(IV)
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[352].
Uranocene has been prepared by treating uranium with cyclooctatetraene at room temper-.ture. The thermal behaviour of uranocene was investigated.
Between 575-680 'ii it sublimed
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[3533.
Lithium hexaalkylu~anate(IV) complexes combined with cyclooctatetraene to form uranocene in good yield [3!&]. The substituted uranocene (20.1) has been prepared by the reaction of uranium(IV) chloride with the cyclobutenocyclooctatetraene dianion [3553. Bis (~-bicy~loo~tatetrae~yl)d~urani~, "biuranocenylene" (20.2) has been obtained, together with l,ll-bis(cyclooctatetraenyl)uranocene, by treatment of bicyclooctatetraenyl :\rith potassium in THF and then uranium(IV) chloride [356]. Uranocene has been reduced with lithium naphthalenide in tetrahydrofuran to give [~(c~~~)~]-L~,',THF. 1WR an,d ZSR data
127
U
d 0
20.2
20.1
indicated that this anion had a sandwich structure and that U(II1) was present [357]. The reaction of uranocene with iodine gave UC 16H.,21q which could be sublimed under reduced pressure.
The infrared spectrum
of the product indicated the presence of a C-I bond and possible use of this compound for the preparation of ultra pure uranium was discussed
[358].
Oxidative-addition takes place at uranium in the bis(r\pentamethylcyclopentadienyl)uranium
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3.59 ;i. j. complex (20.4) was an
effective hydrogenation and polymerization catalyst for alkenes [360].
7% Tk UMe2
UClX
*
+ 20.3
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295'1613, 1'380 Jul.
(1981).
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and IJ. V. Kalugina,
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R. fiI.
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tiaki,
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Lee
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8528~?2,
Prom.
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(Dow Corning
N. pii.
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3s
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c.
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and H. N. Haszeldine,
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H. Vahrenkamp,
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and Idi.3. Rail,
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331.
Commun.,
H. 3eurich
‘13 (1981)
(1981) c17. R. 3oese
(1981)
Chem.
D. Steiert
Chem.,
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327
Chera., 209
Angew.
R. J. P. Corriu Chem.,
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(1981) ilO1.
219
208
Chem.,
20
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P. H. Rieger 265
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Pi. Casarin
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D. Seyferth and M. 0. Nestle, J. Am. Chem. Sot., 103
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D. L. Beach and T. P. Kobylinski, J. Inorg.
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85 (1982) 3026. 342
K. Chhor, G. Lucazeau and C. Sourisseau, J, Raman
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Spectrosc., 11 (198-l)183. I?.H. Kohler, U. Zenneck, J. Edwin and '4. Siebert, J.
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bOC*,
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348
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H. k&,mkuh3., A. Rufinska, R. Berm, G. Schroth and R.
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351
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146
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and D. A. Owen,
L. D. Rhyne,
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Diss.
Abstr.
Hadiokhimiya,
3%
J. T. Killer,
Diss. Abstr,
355
IV! . D. Luke,
356
14 .
357
20
23
Plast.
Int.B,
S. R. Berryhill
(1980) 1375. D. N. Suglobov
and
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358
V. G. Sevastyanov,
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Commun.,
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360
Int. B, 41
V. P. Solovfev,
V. A. Volkov,
209
Coat.
41 (1979) 44.
3%
Chem.,
Org.
R. G. Bowman,
H. Narquet-Ellis, Sot.,
Radiokhimiya, Y. Hirose 232
(1981)
and
5603.
D. N. Suglobov
and
23 (1981) 73.
and G. Gaughan,
J. Chem.
Sot.,
(1981).
R. Nakamura,
and T. J. Marks,
103
V. P. Solov'ev,
P. Rigny
J. Chem.
P. J. Fagan, Sot.,
R. L. BurweII
Chern. COF~~.,
257
(1981).
5%
Q 0
Mrl=cz==c-
CPh2
MIl~C===
(W2
(CO);!
9.7
9.6
9.8
9.9
c 0
Mn
(Cop
9.10
9.27
CH-
CH(t-3u)2
53 carbyne ligands CMe+, CSiMe3+, CPh+ and CNEt2' and the metalContaining fragments (T-CgH5)Mn(C0)2 and Cr(CO)S have been investigated by a nonparametrised molecular orbital method. Calculations were carried out on four carbyne complexes made from these fragments: (?-CgH5)Mnn(CO)2CMe+, (?-CL;H5)~(CO)2SiMe?', (?-C5H5)Mn(C0)2CPh+ and (CO$CrCNtit2+. It was concluded that the orientation of nucleophilic attack on these complexes seemed to be frontier controlled and that the gross positive charge of the substrate molecule enhanced its overall reactivity towards nucleophiles 10.
[I591.
(q-Trimethylenemethane)Fe(C0)3 Complexes Molecular orbital theory has been used in a theoretical
investigation of the energies of low lying electronic states in the 2-methylenecyclopentane-1,3-diyl
ligand (10.1) [16O].
Ph
Fe (CO)3
10.1
10.3
10.2
.->
Fe2(C019
Ph
Ph
20 Oc Ph
Ph (COJLc
10.4
References
p. 128
10.5;
Fe GOI
10.6
54
The stereochemistry of ring opening of 2_phenylmethylenecyclopropane
(10.2) to tricarbonyl(r\-phenyltrimethylenemethane)-
iron (10.3) has been elucidated by stereospecific deuteriurn labelling.
The reaction of 2,2-diphenylmethylenecyclopropane
(10.4) with nonacarbonyldiiron gave the tetracarbonyliron complex (10*5), identified by X-ray crystallography, which underwent ring opening to form the (l-trimethylenemethane)iron ccmplex (10.6). The stereochemistry of the reaction mechanism was snown to be consistent with frontier molecular orbital symmetry considerations _ _
11.
(Acyclii:-?j-diene)Fe(COf3Complexes IJV irradiation of pentacarbonyliron with a mixture of
1,3-dienes and silanes gave mixtures of isomeric hydrosilylation 3 products. The reaction proceeded by way of intermediate (r\ anti-b~teny~)tricarbony~~ron-tr~alky~si~ieon complexes which were accessible by photoinduced addition of R3SiH to (n\-butadiene)tricarbonyliron and which on heating gave similar mixtures of isomeric butenyLtrialkyLsi.licon derivatives [162]. Treatment of the cyclopropenic ester (11.1) with enneacarbonyldiiron led initially to the l-allylcarbonyl complexes (11.2 and 11.3). When these compounds were heated decarbonylation and hydrogen migration occurred to produce the tricarbonyliron complexes (11.4 and 11.5). From this and related work it was concluded that (y3:q'-alLyJ.carbonyL)tricarbonyliron complexes were converted easily into (tri~arbony~)(~4-d~en~)i~on compounds whenever the possibility of hydrogen migration existed 11633. Reaction of the dibromide (11.6) with Fe2(CO)o produced the (r\-3,k-dimethylene-l,S-cycloheptadiene) complex (11.7). Treatment of the latter complex (11.7) with n-butyllithium folloued by water, deuterium oxide OP bsnzaldehyde gave the tricarbonyliron complexes rl1.8; R = Ii, II, CH(OH)Ph] respectively Tricarbonyl(~-2-pyrone)iron
combined with two nucleophiles
in succession to form substituted (y-butadiene)tricarbonyliron Thus treatment with n-butyllithiunl and then methyl-
complexes.
lithium gave tricarbonyl[?-(ZE,&E)-2,4-decadien-6-one]iron. Several reactions of this type were reported and a mechanism was proposed
[165].
Fe
11.1
Fe (co)3
(co)3
11
11.5
.h
Q I
CH2Br
BrH2C
H2C
\
I Fe
CHz
NOI
11.6
References
p. 128
11.7
w3
11.8
56
Irradiation of 2,3-dimethyl-1,3-butadiene with (q-X2= CHCO$ie)Fe (CO) gave the 1\4-di.cne-iron complex (11. ‘1). 4 Reaction of the complex (11.9) with carbon monoxide at >,-30 ' produced a mixture of the tricarbonyliron complexes El
=
R,
(11.10;
R2 = COTMe; Ri = CO2Me, R2 = Hj [IG].
X ‘I’ 11.10
11.9
The (q3-vinylcarbene)iron complex (11.11) was attacked by diazo compounds, N2CHR, where R = H, C02Xt, Eh, to form the (r,-butadienejifon complexes (l?.l%; R = H, CO2&Zt, Ph). mechanism appeared to invol.ve insertion of the of
The
mcthyiene
group
the diazo reagent into the carbene carbon-iron bond [167]* The main product from the reaction of 2,3,5,6-tetrakis-
(methylene)-'j'-oxabicyclo[2.2.l]heptanewith Fe,(COjq was bis(t~ica~bo~iyl~ron~comp~ex (17.13).
The
complex was determined by X-ray analysis.
structure
of
the
this
I of 'The a&i.tio-i
OMe
11.11
11.12
11.13
12.14
trifluoroacetic acid to the complex (11,13) gave initially a 7j3-Ed.lYl Complex then the trans-bis(~3-allyl)isomer high regioselectivity [168].
(11.14) with
T'b electronic structure of the complexes (T-diene)2Fe(CO), where diene = butadiene, dimethylbutadiene and 1,3-cyclohexadiene, has been investigated by He(I) photoelectron spectroscopy. The first seven bands in each spectrum were assigned using INDO calculations based on the ASCF procedure and the transition operator model. Bonding in the ground state of the parent complex (~-butad~ene)~Fe(~O), was discussed5p 691. The natural isotope abundance
Fe N!miRspectra of thirty-five
organoiron complexes, principally cyclic and acyclic (r\-diene)Fe(COj3, have been measured at 2.9 MRz by direct detection. The 57 Fe chemical shift range observed was 3000 ppm and most rBsonantes were at higher frequency than that of pentacarbonyliron which was used as a secondary standard. The 57 Fe shielding was discussed qualitatively in terms of charge distribution in the complexes with very large deshielding effects being observed for cationic olefinic ligands. The shielding in (I-dienejiron complexes was dependent upon ligand geometry and decreased with an Increase in C-C-C bond angle or with an increase in ligand ring size [170]. Moessbauer spectroscopy was used to study the dynamic ProPerties of (r\-butadiens)tricarbonyli.ronfilms on exfoliated graphite (1711. The infrared and Raman spectra of (T-butadienel- and (Y-hexadeuterobutadiene)-tricarbonylirOn have been recorded and
References
P. 128
58 interpreted
[I72-J.
Tricarbonyliron has been used as a protecting group for ‘I,?-dienes in the stereospecific synthesis of insect pheromones. Thus (~-butadiene)tr~carbonyliron was treated with Cl~O~C~~)~C~~~t and AlCl
under Friedel-Crafts conditions to form the (q-diene)-
iron comzlex (11.15) which was converted to the acetate (11.16) in two steps.
Decomplexation with trimethylamine N-oxide gave
the free pheromone, fX)-9,?1-dodecadienyl acetate, of the red Several. related pheromones were obtained in the
bollworm moth. same way
[173].
Fe
w3
11.16
11.15
Cationic polymerization of the (q-butadienejiron complex (11.17) with boron trifluoride etherate gave a methanol insoLuble
/----cf /\
polymer while the monomer (11.18) obtained by thermal
Fe (CO)3
I
F;e
(CO13
59
isomerization of the complex (11.17) was inert to cationic polymerization,
Polymers derived from related (r\-pentadiene)-
iron and -ruthenium complexes were chemically modified to contain the l-ally1 group and metal-metal bonds.
1,2-Polybutadiene and
3,4-polyisoprene combined with pentacarbonyliron and dodecacarbonyltriiron to yield polymers with (q-diene)iron groups in the main chain [174]. The (t\-butadiene)-iron and -ruthenium complexes (11.19; M = Fe, Ru) have been prepared as monomers and were polymerized with cationic initiators to give high molecular weight polymers (11.20; M = Fe, Ru).
These polymers were then protonated using
dry hydrogen chloride to form (y-allyl)metaltricarbonyl groups [I75 1. The tricarbonyliron derivative (11.21) has been resolved and used to prepare the optically active complexes (11.22 and 11.23). These complexes were used to prepare chiral electrophilic cyclopropanes [176]. The carboxaldehyde complex (11.24) has been treated with hydroxylamines to form the nitrones (11.25; R = Me, Ph) which underwent 1,3-cycloaddition with olefins to form the corresponding isoxazolidine complexes
[177]. The electronic effects in the tricarbonyl(y4-diene)iron
derivative (11.26) have been evaluated by pKa measurements on this compound and on the uncomplexed diene ligand. The results
M
(W3
11.19
References
p. 128
11.20
(C02Ple)2
Me0
2
C*CHO
/
lle02C \
Fe
bm3
/
-+ Fe
(CO),
11 .22
11 . 71
Me02C*
Fe
J2
(C02Me
m3
11.23
indicated it
that
reduced
the Fe(C0)
3
group
the electron-withdrawing
by disruption
of the conjugation
aromatic
[178].
Me0
2
ring
c~CHO
was electron
releasing
properties of' the dienyl
of the diene
system
c;roup with the
Me02C
Fe
(COj3
11.24
and that
11.25
61
11.26
mneacarbonyldiiron attacked the pcntaene 5,6,7,8_tetrakis_ (methylene)bicyclo~2.2,2]o~t-2 -ene in hexane-methanol to form the endo,exo-bis(tricarbonyliron) complex (11.27) and the structure of this complex has been determined by X-ray crystallography . The asymmetric arrangement of the two Fe(CO)3 groups was used to induce either stereospecific functionalization of the uncoordinated endocyclic olefinic bond or stereo- and regioSpeCifiC functionalization of one of the two coordinated s-cisbutadiene groups of the complex. Thus hydroboration/oxidation
of the Complex (11.27) gave the _endo,exo-bisftricarbonyliron)bicyclooctane-2-01 (11.28) while cis-deuteration was achieved with D /I%0
in hexane to form the _, endo
exe-complex
(11.29).
Proton~tion'of' the initial complex (12.27) with HCI/Al.Cl /CH2C12 gave the *\3-dienyl cation (11.30) which was quenched wit2 /CH OH to form the tetraene complex (11.31) by 1,4-addition S:ereospecific acetylation of the same complex (11.27) with CH3COC1/AlC13 in dichloromethane afforded exclusively the endo-derivative
(?1.32) which isomerized in solution to the
thermodynamically preferred form
(11.33).
The crystal and
molecular structure of the complex (11.321 was confirmed by X-ray Several related reactions were reported [ISO]. crystallography. The acetol.yses of the brosylates (11.34, 11.35 and 11.36) The acetolysis of the have been studied by 1H I%%? SpeCtrOSCOPy. complex (11.31;)was too slow to detect and that of the complexes (11,3& and 11.36) occurred with retention of configurations From the results it was concluded that homoconjugative stabilization n\-diene-Fe(C0)3 group can of a carbocation by an eXOCYcliC compete with its destabilizing inductive effect [loI]* References
p 128
62
3
11.29
L
Fe (CO) 3
Fe (CO)
Fe (CO13
Ge
m3
wN3 11.32
11.33
63
11.34
11.35
11.36
Reaction of the tricarbonyliron complex (11.37) with Me2As.M [M = Mn(CO)4PMe3, Fe(CO)2(?-C H ), Mo(C0)3(~j-CgH~), Mo(C0)2(r\-C5HS)PMe3, W(CO)3(?-C5HS), 5W?CO)2(?j-C5H5)PNe3 Jgave, for example, the tetracarbonyliron complexes [11.38; M = Mn(C0)3PMe , Mo(7\-C5H 5 )(CO),], (11.39) and (q-C5HS)(C0)3WAsMe2Fe(C0)3?sMe2L [L = Fe(C0)2(r\-CSHS), Mo(CO)2(r\-CSH5)PMe3] [182]. The (r\-butadiene)iron and (y-heterobutadiene)iron complexes (11.40; X = CH, N; L = CO, PPh3, AsPh3, SbPh3) combined with 1,2-bis(diphenylphosphino)ethane (diphos) to form the derivatives Fe(C0) (diphos)diphos. A kinetic study of the reaction suggested 12 an (T\-butadiene)iron intermediate [183]. Friedel-Crafts acylation of the hexacarbonyldiiron complex (11.41) with acetyl chloride or benzyl chloride produced the corresponding tricarbonyliron complexes (Il.@; References
p. 128
R = Me, Ph) [I&].
64
)-VI
O’I’ 0 Fe
(m3
,\/
Fe
(CO)
1"
.37
4
Il.36
0
II.39
11
.i+o
0
/\ 4Fe
11.41
ll.iL2
R
65 12.
(7\-C,+q)Fe(C0)3 Cocondensation of arenes with iron atoms at -196
the complexes Fexlarene)
'C
gave
which combined with hydrogen to form
-cyzl.onexadiene)iron complexes (IS.1;R=H, the mixed (r\-arene)(y Me, CMe3, Me3).
Vihencyclopentadiene replaced hydrogen as the
reagent then the (y-cyclohexadienyl)iron compl.exes (12.2; R = h, Me, CMe3, Me21 were formed
12.1
[185].
12.2
The reaction of 1,2-di-t-butyl-3,4,5,6-tetramethylbenxocyclobutadiene with nonacarbonyldiiron produced the two tricarbonyliron complexes (12.3
and 12.4).
The structures of these
complexes were confirmed by X-ray analysis 11106,1871. The crystal and molecular structure of tricarbonyl(y-1,2di-t-butyl-3,4,5,6-tetramethyLbenzocyclobu~adiene)iron
has been
Ph
Ph
"2.3
References
p. 128
12.4.
66 determined
by X-ray
analysis.
coordinated
in
the
was not
complex
because
the
some
of
ring
its
Atom
due
to
the
as a pure
cyclobutadiene
away from
the
to
the
tendency
energy
OT the
theory
electron
has
The
been
in
both
interpreted
of
monoxide
dienone
to
the
ring
to
retain
(&&D)
determine
tbat
was
in
a structure
close
agreement
[189].
of
solid
(r,-cyclobutadiene)tetracarbonyl-
and liquid
phases
matrix
at
12 OK gave
have
been
recorded
isolated
tricarbonyl
[I91 J. (q,-tetraphenylcyclobutadiene)iron underwent
P(0Me)3] a platinum electrode
pending
paramagnetic
same cations
complexes
methane
in
a
(r,-cyclopenta-
with
(12.5)
and were
intermediates
corresponding
Ph
in
(12.6)
AgBF4
and
neutral
by
oxidation
form
the
L = PPh3, oxidation
+ 1
the
formation
of
corresP(O?4e)j].
of
[N(4-Br.0684)4]PF’6 as
in
the dichloro-
tetrafluoroborate
The cations
salts. the
to
C12.6;
generated
were
(12.6)
the
cation
were
or implicated
(22.7)
from
(n,-tetraphenylcyclobutadiene)iron
Ph
Ph
Ph
Ph
Fe
cations
rl2.i’;
one-electron
dichloromethane
characterized in
complexes
reversible
radical.
hexafluorophosphate as
of
benzene
(y-butadiene)tricarbonyliron
L = PPh 3,
The
compl.ex
middle
) iron
The at
but
[I 901.
Photolysis carbon
the
ring
delocalization
used
results
IR and Raman spectra
molybdenum and
diffraction
was
[I&? J.
and el.ectron
tricarbonyl(r\-cyclobutadiene)iron
with
cyclobutadiene
shifted
resonance orbital
mode
group
regarded
was
superposition
molecular of
a tetrahapto
iron
b-membered
The tricarbonyliron
Ph
Ph Fe
(CO)*L
(W2L
12.5
12.6
tne
comple Ph
Ph
Ph Fe
12.7
X
+
67 and Silver nitrate and in similar oxidations.
Several related reactions of iron and ruthenium complexes were reported b92). Irradiation of monosubstituted tricarbonyl_(n,-cyclobutadiene)iron complexes in the presence of propgne gave isomeric mixtures of substituted toluenes.
The presence of electron-withdrawing
groups on the metal complex produced mixtures rich in the ortho isomer while electron-releasing groups favoured the para isomer [193]. (~-~enzo~yclobutadiene)d~carbonyln~trosy~~ron hexafluorophosphate was prepared by the reaction of (n,-benzocyclobutadiene)tricarbonyliron with nitronium or nitrosonlum salts.
The former
complex underwent facile reaction with RjM (M = P, As; R = Me, Ph) afford the +,-benzocyclobutenyliron complexes f(RjMc8R6)~e(CO)(~~O~~R3~+PF~- by a two step process involving nucleophilic to
addition and carbonyl substitution, In the same thesis the mass spectra of the manganese complexes (12.8; L1 = CO, L2 = Ph3P, Ph?As, Ph7sb; k1 = es, L2 = Ph,P, Ph.As, Ph,Sb) were also
CR'R'
12.8
12.9
A Hammett-Deno indicator acidity study using trifluoroacetic acid-water solutions was used. to determine PI&+ values for a series of tricarbonyl(f\-cyclobutadiene)iron carboeations (12.9; R1 = H, Ph, Me, R2 = Ph, ~-i'4eC6H4, Me). These carbocations were less stable than the corresponding ferrocene systems but more stable than a variety of similar organic and organometallic carbocations
Referencesp. 128
[19s],
I?.
(Cyclic-~-diene)Pe(C0)3
Complexes
(i) Formation ii%flCtiOE
with
Of
acetylenes
the
ITe2(CO)g gave
PhC%CWPh3
the complexes
(1~~ = $i, se, Sn, Pb)
i\ic-Lyle,.
(triphenylsilyl)-j,4-diphenyl-;
where
L = ,i,i;-bis-
,~,~-diphenyi-j,4-bis(iriphenyl-
zermyl.)-; :~,4-b-is(t:riphenjrlsta!-!nyl)-j,;-diphenyl-and ciiphenglbis(triphenylLplur?byl) -cgclo?encadierlone groups
Wefe
removed
the corresponding complexes
by treatment
The i-'hjPl acid
to give
tricarbonyl(~-dlphenylc~~rclo~ ontadienone)i.ron
[I%].
The \-gerlmacyclopentadiene-iron ~-PleG5H4, E-Fe2i.C6FIq, C6F5) have corresponding ment
respectively.
with hydrochloric
Eermacgclocentadiene
of t!le trisarbonyliron
(13.1,
complexes
been prepared
ti =
bt,
by reaction
with pentacarbonyliron.
complexes
.Pn,
030 the Treat-
(13.1, R = Pie, CZ;Ph,
gave the corres?onap-WeCbHjC, 2 -Me,MC 3 ) with tin tetrachloride 2 64 i)ecomplexatiorl of the ing exo- chl.oro derivatives (I3.2.). ligands
r\-germacyclopentadiene
Furt’ner
reactions
complexes
cI
was effected
:!:i;hke3!!0 and 'r'icl
4’
of the tricarbonylf7\-~ermacyclopentauienej
iron
[I971.
inieredescribed
c.I
\\ GB
,kcl
’
’
R
Fe
‘K
Fe
("O)3
UXN3
13.2
13.1
I,.!&-Cyclohexadienes with gemwith pcntacarbonyliron diene)iron
complexes Alkyl
the reactions. while
the C02,Me group
complex
with
comalexes oroducts
to form in order groups
(9 3.3;
to elucidate exertea
directed
the entering
substituents
attack
classical
of the correspondicg
effects
steric
by forming
tricarbongLiron
-created
(2,3-cycloinexa-
directing
group.
R = Me, Ph, CH2Ph) weTe formed
by treatment
‘nave been
the corresponding
in
r;indrance
an ir.cermezliate Thus
the
as the exclusive
1,4-cgclohexadienes
69
Fe
Fe
um3
(CO):,
13.3
13.4
with pentacarbonyliron while the products (13.4; Rl = C02Me, R2 = CH2C02Me; R ’ = Me, R2 = Ph) were each obtained as mixtures of two stereoisomers [Z983. The 3a-azoniaazulene complexes c13.5; R = ii, CHO, CH=CHCOCH3, X = 0; R = H, X = CHCIJ and 13.61 were prepared in
CH=C(COCH+,,
high yield by treatment of the free ligands with enneacarbonyI_-
13.6
13.5
I Fe
H
13.7
References
p. 128
70 diiron.
The tricarbonyliron
(13.7) was prepared
complex
also
[199]. Treatment
of s-
nonacarbonyldiiron complexes. produced 13.9)
Reaction the anti-
they both
triene)iron
the corresponding
of these
complexes
k&en the complexes
rearranged
to give
(13.8 and
(13.8 and 13.9) were
tricarbonyl(r\4-
cyclohepta-
Fe
(CO)
wN3
3
13.8
13.9
Thermal produced
reaction
of l,s-cyclooctadiene
in an ampoule
Reaction
was heated
and the tricarbonyliron
a mixture
of products of I-phenyl-
the phosphole-iron
produced
with
with nonacarbonyldiiron
complex
(13.10) was isolated
[202]. or I-t-butyl-3,4-dimethylphosphole
complexes
the corresponding
(CO)9
Fe
[201 .
tricarbonyl(l-l,S-cyclooctadiene)iron
1,5,9-Cyclododecatriene
with
nonacarbonyldiiron complexes
[200].
Fe
from
with
tetracarbonyliron
with
and s-norcaradieneiron
respectively.
heated
or &-tricyclo[3.2.O.O]hept-6-ene
produced
dimers
(13.11 and 13.12) respectively (13.13; R1 = R2 = Ph; R1 = R2 =
The structure of the complex t-Bu; R' = Ph, R2 = t-Bu). = R2 = The two Ph) was determined by X-ray analysis. RI phosphole strongly
rings
adopted
folded
a head
to tail
Bis(~5-heptamethylindenyl)iron
selective I-ene
cyclopentylation
of the complex similar
and iron(I1)
with
by dehydration to form
syntheses
were
has been
chloride
(n,-cyclohexadienyl)iron
followed
and they Were
[203].
heptamethylindene The
disposition
(13.13;
cation
prepared
(13.14)
underwent
regio-
l,Z-bis(trimethylsiloxy)cyclopent-
and dehydrogenation
the 2-arylcyclopentenone reported
from
[204].
(2051.
with
breakdown
(13.15).
Several
71
Fe
13.13
13.12
The rates
of
reaction
of
pentane-2,4-dione with a range of
t~~ca~bo~~~(~~ -cyclohexad~enyi)~ron cations (‘13.16;R = H, He, OMe) and for example (13.17; R' = Me, R2 = R3 = H; R1 = R3 =H, R2 = Me*f R' = R3 = H, R2 = OMe; R' = CO Me, R2 = R3 = H) have 2 been obtained under pseudo-first-order conditions. The rates
13.14
13.15
ii1
R2
7s-.
\
R
.__'
Fe
Fe
(CO)3
Km3
13.17
13.16
were
affected
position.
by the nature
For example,
and a 3-methoxy The enolate
group
of the substituent
a 2-methoxy
a slight
(q-cyclohexadienyl)lron anions Me
at the methylated
group
acceleration cation
caused
(13.18)
,- ‘._s
Me0 q Fe
Mm3 Fe (CO)3
13.19
Fe (CO)3
13.20
combineu
dienyliun: terminus
!
OH
retardation
[2~6].
1'
13.18
and by the
with
in a highly
73 regioselective reaction which was of importance in steroid and terpene synthesis.
Thus the enolate anion methyl 2-oxocyclo-
hexanecarboxylate gave the product (13.19) in 97% yield.
The
complex (13.20) was obtained in the same way and X-ray crystallography was used to determine the crystal and molecular
:,: ?I structure [207].
Reduction of the tricarbonyliron cation (13.21) to the
cyclohexadiene complexes (13.22 and 13.23) by a series of metal
1
‘.d’
Me
Fe
Fe
W3
Fe
(CO)j
13.21
NO)j
13.22
13.23
hydrides became less regioselective at lower temperatures.
In
contrast reduction by 9-borobicyclononane became more regioselective as the temperature was lowered [208]. The absolute configuration of the salt (13.24) has been defined and it has been used for the asymmetric synthesis of the x-disubstituted cyclohexenone (13.25) [209]. Alkylation of the (r\-cyclohexadienyl)iron cations (13.26; R1 = H, Me, OMe) with alkyllithiums, R2Li, where R2 = We, Pr',
+ I =v Me
PF6-
0
\
‘\
r
co2Et
bo2Et
13.24
References p. 128
13.25
74
Fe
Fe
(CO)3
(COJ3
13.27
13.20
13.26
Bun,
But,
in chloroform
at -78 'C gave
(y-cyclohexadiene)iron Pr', Bun,
But).
R1 = OHe)
gave with
(13.28;
(13.27;
products
In addition FriLi,
R = Pri, Bun,
was not observed
Fe
W3
But)
attacked
R1 = H, He, OMe; R2 = he,
to this product,
BunLi
and ButLi,
and the expected
by carbon
nucleophiles
gave a mixture
13.3:
rather
than the expected
and 13.32)
also underwent
The cation
(13.33) has been
of isomers
with
a variety
of the complex
tricarbonyliron
group
cyclohex-2-enone
of nitro-
a S-exo-nitromethyl
treated
NaCH(CO2l4e)2
have
been used The
R = OAc,
carbon
removal
of the
5-substituted
to provide
a route
atom corresponding phthalimido)
were
to give the (r\-cyclohexadiene)iron
Decomplexation
and treatment
the derivative
of the
a mixture
(ni-cyclohexadienylium)-
03S.C6114.Ne-4,
R = OAc, 03S.C6R4."'e-4,
nroducts.
R = phthalimido)
and subsequent
alkaloids.
(13.36;
(13.37;
Treatment gave
the corresponding
the quaternary
iron cations with
to be synthetically
cation.
[%I%].
complexes
containing
in Aspidosperma
acid gave
(13.30,
tricarbonyl-S-exo-
of nucleophiles
(13.34)
produced
(13.35)
Tricarbonyliron to compounds
princinal
shown
to the S-cyclohex-2-enone
(t3.33)
complexes
products.
The anion
to form
(13.29)
[Zll].
equivalent
to C-20
addition
addition
of the xetones
(2-oxobut-3-enyl)cyclohexa-l,?_dieneiron.
cation
regioselectivity
to give
ketone
derivative
(1j.26; products
tetrafluoroborate
Thus methylvinyl
methane
the cation
the isomeric
[210].
Tricarbonyl(q-cyclohexadienyl)iron was
the corresponding
with
(13.38)
phthalimido)
of the product aqueous
[213].
as the
(13.37;
methanolic
oxalic
\ \ / r G+ oi3t
BF -
4
0
O
+
\ /
Fe
Fe
um3
(cW3
13.31
13.30
13.29
0 OEt
+
\/ P Fe (CO
)3
13.32
0
Fe(C013
b
I’ --. R
cl I
R
Fs(CO),
13.33
13.34
13.35
The cations [($-dienyl)Fe(C0)3]+, where dienyl = C6H7, C6H60Me-2 and C7H9, combined with E-toluidine in acetonitrile to form adducts such as the (T-cyclohexadiene)iron complex (13.39). A
kinetic study of the reaction suggested that a two-step
References p. 128
Fe (Co+
T3.36
13.37
NH
Fk (co+ I 3.38 mechanism
was
E-toluidine
13.39
operating
with
to the dienyl
initial
reversible
ring followed
addition
by rapid
loss
of
of a proton
[214]. Tricarbonyl(q-cyclohexadienyliu.m)iron attacked
by anions,
JO-, to give
complexes
(13.40; R = H, Me,
binuclenr
products.
group
R and the reaction The cation
1,2,4-trimethoxycorresponding benzene were
Yields
gave
were
the tricarbonyliron for
in aduition
these
reactions
to
by the nature
of the
[215].
treated
with
1,3,5-,
1,3- and 1,4-dimethoxy-benzene
r\-diene complexes,
obtainec!
determined
conditions
was
cc\-cyclohexadiene)iron
But, Ph, SiMe3)
(13.42) has been and
the
tetrafluoroborate
For example, derivative and were
I,,?,?-, to give
the
1,2,4-trimethoxy-
(I3.41). interpreted
Rate
data
in terms
\iz;
OMe
OR
I
Fe
(COf3
73.40
13.41
of an electrophilic substitution mechanism that involved rapid preequilibrium formafian of aTT-complex followed by rate dstsrRapid proton mining rearrangement to a tieland-Gype s-complex. loss than gave the products [216], The nucleophilic attack of substituted pyridines on the tricarbonyl$-cyclohexadienyl)iron subject of a kinetic investigation.
cation (13.42) has been the The products were pgridinium
adducts (13.43; R = H, 2-Me, 3-Me, &-Me, 2,5-Ne2, 2,6-Me2, The rate of the second 3*54e2, 2,4,&-Me3, 4-Ph, Z-CR, 3-m). order reactions showed a marked dependence on pyridine basicitg. However, blocking of the 2- and 6-positlons of the pyridine by methyl. groups caused steric retardation. The corresponding
reactions
of tine cations
The tropylium tetraene)iron
[(~~-2MeOC&H6)Fe(C0)3]f
were
[(~5-C7R9)3'e(CO)3]+
ion
compared
attacked tricarbonyl(n,-cycloocta@+I+ the neutral complex (13.44) which contained
to form
a y-styrylcycloheptatriene indicated
that
was derived group
molecular X-ray
ligand.
Mechanistic
the cycloheptatriene
from
was formed
the tropylium
ring while
ion.
(13.44)
ti?e phenyl
The crystal
and
(13.4.4) was confirmed
of the complex
crystallography
proposals
ring in the complex
the cyclooctatetraene from
structure
and
[217].
by
[218].
Fe
w3
Reaction
of the close-carbaborane
2,3-Me2-2,j-C2BgHq
(r\-I$-cyclooctadiene)(?_cyclopentadienyl)iron toluene, ether
o-xylene
produced
complex. by X-ray 13.
The
or with
the corresponding6(q6structure
(ii) Spectroscopic The crystal
determined
by X-ray
these
PPh3] have
3' depopulation
L decreased orbital. model
rather
complexes
been recorded
was established
LUMO
Studies
of the
(y-cyclohexa-
L = CO) have been
The I3 C NIW spectra
of
[I3.45; X = H, OMe, L = P(OMe) 3' and interpreted in terms of as the T-acceptor
than the expected
An explanation
[220],
structures X = H, OMe,
crystallography.
of the diene
complex
and Physico-chemical
(13.45;
and the related
in petroleum-
arene)-close-carbaferraborane
[219].
and molecular
complexes
in benzene,
of naphthalene
of the 7\ -toluene
crystallography
diene)iron
AsPh
an excess
with
has been
enhanced
proposed
strength
population
using
of of the
a pictorial
KO
79
\e/ X
Fe
(CO)2L
-;2c-$JMe M;;p OMe Fe
Fe
NW3
(CO+
13.45
The crystal and molecular structure of bis[tricarbonyl(y-cyclopentadienone)iron]hydroquinone has been determined by X-ray methods.
The mo1ecul.e contains two tricarbonyl((-
cyclopentadienone)iron groups linked to hydroquinone by hydrogen bonds [221]. The structure of (~5-1-methyl-4-isopropylcyclohexadienyl)tricarbonyliron hexaf'luorophosphate has been determined by The cyclohexadienyl ring had a sofa conformation
X-ray analysis. [2223.
The thermal rearrangement of the (T-2-pyrone)iron complex (13.46)
to the isomer (13.47) has been investigated.
The crystal
and molecular structures of both complexes (13.46 and 13.47) have been determined by X-ray crystallography and a mechanism involving 3 -vinylcarbene)iron intermediate and a novel I,&-oxygen a (IJ
shift has been proposed [223]. The crystal and molecular structures of the (r,-cyclodeca-
Fe
(cm3 13.48
iteferences
p. 128
80 tetreene)iron
compl.ex (13.48) has beon
cr:Jstallo:~Taphy.
The tricerbonyliron
determined group
by X-ray
:;as bonded
to the
cis-3,5-diene rxG.t or” the ligand [2?bL). g_&..g, The XS,? s net tra of (1-7 , j-eye looctate traene ) iyGi3iij) ( -1,3-~~~~100c~~atetraene~-~'e(c0)3-
? recorded Tesided
and -Fe(Cti),,;‘Phj nave been
It was concluded
?nd interpreted.
in the cyclooctatetraene (n,-‘l,s-
:GLi spectra
for
showed
the unpaired
that
The application
Co-,
portion
t1;s.tthe oi:d electron
and 3, 3-cgclooctadicnej electron
of Frontier
(fi,-CLzii5)Co_.~
was predominantig
Orbital
?he
of r;he molecule.
theory
metal
centred
to cycloaddition
reactions of some tricarbonyliron complexes ‘has been investigated. 1 H iE;i spectroscopy showed that the reaction of totsacyanoethylene
with
13.49
the azepine
complex
(l.?.!.g4) gave
13.50
Fe
Fe
(co)3
13.51
-I 3.52
initiaily
the
81
1,3-addition product (13.50) which isomerized i;o the l,t3addition product (13.51). The initial formation of the I,?addition product Was in agreement with Frontier Orbital theory [226]. A kinetic study has been made of the addition of tetrato (y-cycl_oheptatriene)iron complexes (13.52; RI = H, CCMe, CHO, R2 = R, R1 = H, R2 = COMe) and to tricarbonyl(n,-cycIoheptatrienone)iron in several solvents. The tricarbonylcyanoethylene
iron group activated the complex and the reaction mechanism involved neither ionic nor free radical intermediates.
In one case (13.52; R1 = cH0, R2 = H) two parallel reactions were in competition [227]. The thermal isomerization of tricarbonyl(~-cyclohexadiene$-exo-h-d )iron (13.53) at 134 'C has been studied in order to --7
elucidate the mechanism of 1,5-hydrogen s‘hifts. Identical initial rates of 1E incorporation into the I- and 2-positions of the cyclohexadiene ring were observed.
These findings are
consistent only with a mechanism involving two sequential l,j-shifts of deuterium endo to the metal [228]. Oxidative cyclization of the (T-cyclohexadiene)iron complex (13.54) with anhydrous iron(II1) chloride on silica gel gave the tricarbonyliron complex (13.55) containing a tricyclic ligand. This reaction was in contrast to the behaviour of alcohols and (T-dienefiron complexes towards iron(II1) chloride [229].
OH
H
d7
d \/
I t
Fe (CO)3
13.53
References
p. 128
Fe (CO):,
82 The
(v-cyclohexadiene)iron
-H ) underwent
R"=p
concentrated
sulphuric
iron cation
(13.57;
Ii1 = H, R2 =V,-H) was
discussed
complex
acid catalyzed acid
to form the
R = II, Me).
(13.56;
Rl = H, CO$Ie,
decarbonylation
with
(r,-cyclohexadienylium)(? 3.56;
Iiowever, the complex
was unaffected.
The mechanism
of the reaction
[230].
_
r
+
R ,.--a : '._-
'P E'e
Fe
(COj3
wN3
13.5;6
13.s7
13.
(iii) General Birch
Chemistry
and co-workers
superimposed
lateral
have
control
structures,
by attachment
to olefinic
systems.
discussed
of reactivity,
of transition
The reactions
(T-cyclohexa-1,3-diene)iron
derivatives defined
substituted discussed
were
aryl cations in some detail
Elimination from
the diene
were
treated
corresponding Reaction
of both complexes
with
P(OPh)3]
were
and the trimethylsilyl
(13.58 and 13.59)
occurred
tetrafluoroborate
complexes
Related
and some cyclohexadiene
an ethylenebenzenium
cations,
when
to give
(13.60 and 13.61)
eta-7,9-diene
with
group
they the
(Z-321.
(benzylidene-
or Fe2(CO)
L = CO).
tetrafluoroboric
the derived of specifically
[231].
triphenylmethyl
The tricarbonyliron with
and
derivatives
tricarbonyl-
especially
as equivalents
the hydride
of dispiro[2.0.2.4]d
(13.62;
stereochemistry
or as cyclohex-2-enone
tricarbonyliron
acetone)tricarbonyliron complex
of
metal. carbonyl
of substituted
dienyliron
salts which
the concept
complex
gave the tricarbonyliron 9 complexes c13.62; L = i?Ph3' derivatives were prepared also.
(13.6~; L = CO) underwent
acid to give ion
[233].
the first
complex
reaction (13.63)
of
83
OSiMe
3
\P/
OSiMe3
Fe
w3
m3
13.58
13.59
O-BF-
3
/ P
0
-
Fe
mu3
(co)3
13.60
13.61
/\ F 13.62
BF -
4
13.63
Reactions of the T-enyl complexes
[(y5-C6H7)Fe(C0)3
[(y5-C7H9)Fe(C0)3]BF4, [('\~-c?H~)F~(CO)~]BF~, C[(S.l.O)? CgRq]Fe(CO)3jBF4, [(T\~-C~H~)F~(CO)~]BF~and [(q7-C7H7)Moo(C0)3]BF4 with selected anionic nucleophiles have been investigated [234].
References p. 128
84
The l-cyanocyclohexadiene
complex (lj.61L;r(= CN) was
treated with hydrogen chloride and methanol to give the methyl iminoes'cer (13.65). base i;ave
the amide
'Treatment of i;heiminoester (Ij.;5, with (1 j,Si+;
13.64
d = COX. ) and co::aensation with the 2
13.66
13.65
appropriate nitrogen compounds afforded the heterocyclic derivatives Z-(2-cyclohexadienyl-2,2-irontricarbonyl)imidazoline-2, -benzoxazole, -benzimidazole and Z-phenyl-S(S-cyclohexadienyl-S,S_irontricarbonyl)-l,j,4-oxa~iazole. reactions of \-cyanocyclohexadiene
derivative 113.66)
Some
xei?e alao
investigated [235% The symmetrical. 3-methoxy cation (13.67) has been prepared from tricarbonyl(~,-l,~-dimethoxycyclohexa-1,~-diene)iron by treatment with trifluoroacetic acid. The cation (I 3.6’7) was shown to be synthetically eq.uivalent to a meta-methoxybenzene cation OP to a S-cation
of cyclohex-2-enone.
OHe
The prer,mation
cl= 1 0
,
,I
13.57
13.68
‘i3.69
85 of
tricarbonyl(l-cyclohexa -2,4-dienone)iron was also described
and nucleophilic reactions at the l-position of this complex were investigated
[236].
Stereospecific reactions of' tricarbonyl(y-cyclohexadienyl)iron salts, derived from unsymmetrically substituted tricarbonyl(y-cyclohexadiene)iron complexes, have been used to direct the .f'ormationof new chiral centres at carbon and so to define absolute configurations by chemical correlation with the terpenes cryptone and phellandrene.
For example, (lS)-(+)-tricarbonyl-
(n,-I-methoxy-1,3-cyclohexadiene)iron (13.68) has been correlated with (R)-(-)-cryptone (13.69) [237]. The (y-cyclohexadiene)iron complex (13.70; E = CH2), obtained by a Wittig reaction on the (T-acetylcyclohexadiene)iron complex (13.70; E = O), was protonated with fluoroboric acid to give the salt (13.71). Acetylation of the same complex, (13.70; E = CH,), with one mole of an equimolar mixture of AlCl, and Me
I CHCH2COMe
k
BF 4
CC. I' , ‘.r ij Fe (cO)3
13.71
13.70
2
13.73
References
p. 128
COMe
13.72
+
PF6-
86 MeCOCl
gave
three
products,
the salt
(13.72)
(13.73;
(y-cyclohexadiene)iron
complexes
R1R2
of 14, 26 and 4.5%
= =CH2)
in yields
Me0
and the
R1 = lie, R' = Cl; respectively
(CH2)nC0214e
CH
[238].
2
\ (CH& Fe
Fe
(co+
(COj3
13.74
13.75
\
J
13.76
0
v $
13.78
0
CH(CH20H)2 ." ___
0
0
0J
Fe (GO)j
13.79
87
H CH2OH H
13.80
13.81
(y-Cyclohexadienylium)iron complexes have been used as intermediates in the synthesis of azospirocyclic compounds.
Thus
the (r\-cyclohexadiene)iron complexes (13.74; n = I, 2) were converted to the (y-cyclohexadienylium)iron intermediates (13.75; n = 1, 2) by sequential reduction, tosylation and hydride abstraction. The intermediates (13.75; n = 1, 2) were treated with benzylamine and subjected to demetallation and hydrolysis to give azaspirocyclic enones (13.76; n = 1,'2) [239].
In a
related sequence of reactions the (T-cyclohexadienylium)iron complex (13.77) was stereospecifically converted to the trichothecane intermediate (13.78) [240]. Stereospecific cyclization of the (n\-cyclohexadiene)iron complex (13.79) using T1(02CCF3)3 in the presence of sodium carbonate gave the cis-hydrindene complex (13.80) which underwent acetylation and decomplexation to form the product (13.81; Y = 0). A similar cyclization was used to obtain the product [13.81; Y = C(CO,Me),] [241]. A stereocontrolled total synthesis of a 12,13-epoxytrichothecene analogue (13.82) has been achieved using the hexafluoroThe synthetic route described illustrated phosphate salt (13.83). the usefulness of the Fe(C0)3 group for diene and dienol ether protection [242]. The conversion of the diastereoisomers (13.&;
R =M-
P_C02Me) to steroid precursors has been described [243]. Oxidation of the complexes (13.85; oc-cO2Me, OR =K-OH; p-C02Me, OR =B-OH)
References p. 128
was effected with either thallium(II1)
or
+
Me
I I Q a
\
’ *_
,
OMe
PP6-
I;'e
(W3
13.83
13.82
OMe
Me0 Fe
13.84
trifluoroacetate corresponding complexes
or iron(II1)
cyclic
and related
b,k-disubstituted
isomers
the j-exo
zbably
Catalytic
were
by phosphines
readily
and in methyl
gave
the bicyclo[j.2.0]
to the cycloheptatriene
into
[2441. -cyclohepta7 either S-exo or s-end0
direct cyanide
via a metal-assisted
amounts
The latter
converted
tricarbonyl(n,-cyclohepta-
In dichloromethane, isomer
gel to give the
to the tricarbonyl(
of phosphine-substituted
was formed
izing
addition
cation
:,3-diene)iron. gave
compounds
on silica
(13.86 and 13.67).
cyclohexa-2,S-dienones
Hucleophilic dienylium)iron
chloride
derivatives
complex
(13.89).
at the ring
the 5-w
pathway
of acid or base were nona-2,4-dien-B-One
attack
isomer
[2'45].
effective complex
Kechanisms
in isomer(13.66) involving
89
(c0j3 Fe
OR \
I 0-b Me
C02Me
Me
C02Me
13.86
13.85
Fe
Km3 13.87
13.89
References
p. 128
13.88
so vinylcycloheptatriene reactions
intermediates
were used
to explain
[246-j.
The
2-oxyallylcation
2,i+-dimethylpentan-j-one
(13.90),
generated
from
and enneacarbonyldiiron
(13.91)
whose
oxidative
structure
degradation
was
confirmed
of the adduct
13.90
gave
group.
compound
Similar
13.92
were
had
inserted
carried
out with
tricarbonylC8-(4-chlorophenyl)-8-azaheptafulvene]iron tricarbonyl[(N -ethoxycarbonyl)azepine Protonation
with HPF'o, HBF
(v-cyclooctatetraene)ruthenium
/\ 8 I 0
or CF3C02H
‘L.!
PF6-
and (I-arene)-
the corresponding
+
e
0 .d
13.93
of
gave
I RLl
13.94
a
[247,248].
3iron
?omplexes
i I-
The
analysis.
(13.91) with o-chloranil
(13.92) which
reactions
treated
a 1 :I adduct
by X-ray
13.91
the iron-free
carbonyl
2,4-dibromowhen
tricarbonyl(q 4 -cycloheptatriene)iron,gave
with
the
PF6-
[(ij-arene)(l-5-r\-CSH9)Ru]+ cations (arene = mesitylene, hexamethylbenzene or t-butylbenzene) which were isolated as PF6 or BF salts. The mesitylene and hexamethylbenzene species
4
isomerized on warming in organic solvents to [q- arene)(I-3:6-7-q-C8H9)Ru]+. The structures of the isomeric \-cyclooctatrienyl complexes (13.93 and 13.94) were determined by X-ray analysis 12493. Cxidative dimerization of tricarbonyl(T-cyclooctatetraene)iron (13.95) gave the dication (13.96) which was attacked by triphenylphosphine to form the (?-bicyclooctadiene)(r\-bicyclooctadienyl)diiron cation (13.97; R = Ph) and this rearranged to the intermediate (13.98) before undergoing further addition of triphenylphosphine to give the bis-phosphonium salt (13.99). Both triphenylphosphine groups were displaced by hydride on treatment with sodium borohydride to yield the binuclear (I\-cycloheptatriene)iron complex (13.100).
The crystal and
molecular structure of the bis-phosphonium salt (13.99) was determined by X-ray crystallography. Wnen triphenylphosphine was replaced by tributylphosphine then the dication (13.97; R = Bu) gave the bis-phosphonium salt (13.101) which was reduced with sodium borohydride to the (r\-bicyclooctadiene)iron complex (13.102) [250]. The (y-cyclooctatetraene)iron complex (13.95) underwent electrochemical or chemical oxidation to the reactive radical cation (13.103) which was followed by isomerization to the bicyclic species (13.104) and dimerization to the binuclear dication (13.105; L = CO).
The crystal structure of the cation
[13.105; L = P(OPh)3] as the PF6- salt has been determined by Borohydride ion reduced the cation X-ray crystallography. (13.105; L = CO) to the neutral complex (13.102) while bromide ion caused reductive C-C coupling to form the complex (13.106). This last product (I3.106) was converted to the binuclear complex (13,107) with enneacarbonyldiiron Ligand substitution and nucleophilic
[251]. I?eaCtiVity
in
tri-
carbonyl(r\-cyclooctadienylium)iron (13.103) has been studied. Attack by cyanide ion gave the carbonitrile (13.109) and the cyclooctatriene)iron complex (13.110) while triphenylphosphine (Y gave the phosphonium salt (13.111). Methoxide ion led to the -cyclooctadiene)iron complex (13.112) while iodide gave the (I (l-cyclooctadienyl)iron complex (13.113) which was converted
Referencesp. 128
/\ 0
92
”
-
Fe
FejCO)
(GOI3
I-
(CO)3F~
3
PR
13.96
13.95
3
I
p&q
3
Fe(W3
(CO)3Fe
I
13.98
ie(C0) 13.99
PPh3
3
Fe(CO)3
13.97 mu I 3
(COJ3Fe
NaBH
4
13.102
\
(CO13Fe
13.95
/\ \0/
-e
. 6 93
+
+
l’
:
I
*
(W3
NOI
13.103
I
Fe
ma3
13.104 /
Fe (CC1). 2+ 3
Fe
Kxo2L 13.10 ‘5
13.106
I
Fe2(C019
\/ \/ ($3 Fe
Fe
m3
mN3
13.107
References
p. 128
8’
Fe
Fe
\/ \/ m
l__.’
H-
b 13.102
d
94
\3/
PPh3 Fe
Fe
Fe
(CO13
mx3
(cm3
13.108
13.111
13.712
I\
Fe
Fe
Fe
NOI
13.109
13.113
13.110
CN-
:0. , /
‘..__-’
Fe
(Cop
13.114
OMe
95
with cyanide ion to the product (13.114).
Several related
reactions were reported [252]. The electron rich cyclooctatetraene complexes (y4-C8Ha)Fe(C013, (7\4-C8H8)(y5-C5H5)Co and (r\4-C8HB)(\5-C5H5)Rhhave been treated with unsaturated cationic derivatives of rhodium, iridium and palladium to form dimetallic products. For example, reaction of the iron complex with y4-cyclooctadienerhodium tetrafluoroborate gave the cation (13.115).
All the complexes
prepared were characterised by 13C NMR spectroscopy [253]. TsO
H
&I-
Fe
(CO13
13.116
13.115
(y4-Cyclooctadiene)(q6 -cyclooctatriene)ruthenium has been shown to behave as a selective hydrogenation catalyst with some polyenes.
For example, cycloheptatriene was hydrogenated
at room temperature under one atmosphere of hydrogen and it was possible, by variation of the solvent, to form monoenes
[254] -
The rates of solvolysis of the complex (13.1161 and the corresponding free ligand have been measured. The presence of the tricarbonyliron group increased the rate of methanolysis. This was believed to be the first example where iron complexation had increased the rate of reaction at a remote site where there was no possibility of direct metal participation 14.
[255].
[(?+H;)Fe(‘+&~ The ligand-exchange reaction between arenes and ferrocene
has been utilized for the selective complexation of aromatics in petroleum. The aromatics were identified by pyrolytic mass spectral analysis and by thin layer chromatography of the
References
p. 128
96
-arene)(s\5 -cyclopentadienyl)iron (15 exchange reaction.
cations formed in the
There was good agreement between the two
sets of data [256]. L&and
exchange reactions between ferrocene and g-, g- and E-toluidine gave the corresponding (n,-cyclopentadienyl)(q-toluidine)iron cations (14.1) which underwent deprotonation with potassium t-butoxide in TBF to form the zwitterionic These complexes (142) were effective as complexes (14.2). nucleophiles in reactions with methyl iodide, carbon disulphide, acetyl chloride, propionyl chloride and benzoyl chloride. The products (14.3; R = I%, At, Ph) were obtained from the three acid chlorides
[257].
t NHCOR
Fe
Fe
PP6-
6 0
14.2
Ligand exchange in
(+)-1,2-
14.3
(a-ketotetramethylene)ferrocene
(14.4) was carried out in benzene in the presence of aluminium chloride. Retention of configuration occurred and the optically
6;; 0
0
Fe
Fe
14.5
97
active salt (14.5)
was isolated with an optical purity close
to 100% [258]. Ligand exchange has been effected in a series of ruthenocenes (14.6; R' = Et, COMe, H) by treatment with an aromatic hydrocarbon in the presence of aluminium chloride-aluminium
Q 0
Q
The corresponding cations (14.7;&=
powder.
0
RI
RI-
Et, COMe, B;
+
Ru
RU R3
6
0
R2-0
0 R4
14.6
14.7
R* = R3 = H, R4 = H, Cl, Me; R2 = R3 = J34 = We) were formed and these were isolated as the hexafluorophosphate salts [259]. Ferrocene has been attacked by [2.2]paracyclophane in the presence of aluminium chloride and aluninium powder to form
Q
2+
0
Fe
PF6-
0
Fe
2PF6-
0 @ Fe
14.8
References
p. 128
14.9
98
the
(v-paracyclophane)iron Oxidation
of the
with N-bromosuccinimide cation Yhen
(14.11)
cerium(IV)
cation
(14.11)
Oxidation toluene
of
complexes
(I-cyclohexadienyl)iron gave
and the free was
a mixtare ligand
the oxidizing
and benzene
Q
agent
(r\-benzene)(\-toluene)iron
complex
of the
PhCMe2CN
was obtained
as the only product
#‘--
(114.8 and 14.9)
[r60]. (14.10)
(n,-benzene)iron
in the ratio
then a mixture in the ratio with
1:s.
of the 1:l.
ceriurn(IV) gave
[261].
+ CMe2CN
'*__
Fe
Fe
14.10
14.11
The electronic
absorption
(T-cyclopentadienyl)iron mesitylene,
tetralin,
and the corresponding interpreted
14.13) 4
3
biphenyl, neutral
of a series arene
naphthalene complexes
in the
has been
have
of
(T-arene)-
= benzene,
toluene,
and phcnanthrene, been
recorded
(r\-cyclohexadienyl)iron complexes (14.12 13 C NMR investigation. in a
compared
-
9 :'--'._.
2
Fe
(CW3
14.12
where
[262].
Bonding and
spectra
cations,
14.13
and
99 In the tricarbonyliron complex (lL+.lZ)
the Least shielded carbons
were C(2,4) while in the ( -cyclopentadienyl)iron complex
7 were similar [2633. (14.13) C(2,3,4) The I3 N l@B spectra for seventeen (?-arene)(~-cyclopenta-
(14.74; X = H, Me, Et, Pr', But, Ph, OPh, COPh, OMe, C02H, NH2, NH +, NMe2, CN, NO23 F, CL) have been 3 measured and analyzed in detail. The chemical shifts were interpreted qualitatively on the basis of ligand-metal interactions. 13 C NMR spectra were recorded for seventeen polgdienylliron salts
substituted arene complexes,
E(l-arene)i?-CsHs)Pe3PF6 [264]-
r
-4
0
-IR
0
PF6-
cf,
BF 4
Ru
0
14.14 NuCleOPhiliC
14.15 replacement of chlorine in (l-chlorobenzene)-
(~\-cyclopentadienyl)ruthenium tetrafluoroborate occurred when it was treated with methanol, pipe&dine
or ammonia to give
corresponding ruthenium complexes (14.15; R = MeO, piperidino, NH21 [265]. The nucleophiZic displacement of chloride by phenoxides
(34.17; R = H, 3-$ h-Me, 4-Ph, 3-CQ$k,
3-C%, ~-BP)
in the
(r\-benzenejiron complex cations (14.16; R = H, Z-, 3-Me) has been the subject of a kinetic investigation. Hammett e values were determined for the three cations (14.16) as 3.16, -3.55 and -3.01 respectively, The reaction mechanism was interpreted in terms of Meisenheimer-type intermediates
[266].
The azido complex (14.38; X = N3) has been prepared by the chlorobenzene derivative (14.18; X = Cl.) reaction of the ,\6with sodium azide. Pyrolysis in vacuum or irradiation of the complex (q4.18;
x = 83) gave (i\b-aniline)(~5-cyclopentadienylf-
iron hexafluorophosphate
References p. 128
(14.18; X = NH2) together with some
100
+
R
R
Cl 9 Fe
m
6 0
o-
14.17
lit.16
cyanoferrocene. terms
The formation
of a phenylnitrene
of these products
complex
was
explained
in
[267].
The addition of LiCH(CN3)CIJ to the cation (l&.19) gave 5 -cyclohexadienyl)(r\ 5 -cyclopentadienyl)-iron initially a (T\ complex
which
mediate
(14.20)
was oxidized and
by N-bromosuccinimide
then to a mixture
to the inter-
of the cyanides
(l&.Ll)
in the presence
of 6-
3.
[ 263
Photolysis or 2-electron
(14.22)
of the cation donor
ligands
resulted
in replacement
of the
7-E -X y lene ligand with one 6-electron or three %-electron donor ligands. The 6-electron donor ligands were cycloheptatriene, cyclooctatetraene and 2,2-pnracyclophane and the ?-electron Y6donors were trimethyl- and triethyl-phosphite [269]. Irradiation
of
hexafluorophosphate by visible
light
was heated
with
powder
(\,5-cyclopentadienyl)(~6-E-xylene)iron and
gave
[2.2]p aracyclophane
the iron complex
[2.2]p aracyclophane
and aluminium
chloride
in dichloromethane
(14.8).
Jnen ferrocene
in the presence
the dication
of aluminium
(14.9) was formed
[270]. (l&.23; R1 = H, R2 = Me,
The ketones
R1 = Me, R2 = Ph) have secondary Acids
alcohols
were reduced
been
transformed
or pinacols similarly
alcohols.
The electroreduction
organoiron
group
group
rather
chemical
into
by cathodic
to give
reagents [271].
the corresponding
reduction
the corresponding
was activated
and it was regiospecific
than on the ring,
Ph; R1 = R2 = Me;
in contrast
on mercury. primary
by the cationic
on the functional to the reduction
with