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Organic reactions of selected π-complexes annual survey covering the year 1974
.
ORGANIC R?ZACTIOZ3 OF SEL?ZCTED~COMPLMES ANNUAL SURVEY COVERING THE YEAR 197%
BERNARD
W. ROCKETT
Department
and GECRGE
of Physical
MARR
Sciences,
The Polytechnic
Wolverhampt on, WV1 1LY (Great Britain)
CONTENTS 198
1. Review6 2. General
199
Results
3.. (')-C5H5)2Ti
202
4. (q-C6H6)Cr(CO)3
203
(i) Formation
203
(ii) Spectroscopic (iii) General
and Physico-chemical
Studies
206 213
Chemistry
217
(iv) Analogues
220
5. (pC6H6)2Cr 6. ~p%p7)Cr(CO13~*,
224
<7-C7H8)Cr(CO>3
228
7. opC5H5MC0)3
228
(i) Formation (ii) Spectroscopic (iii) General
and Physico-chemical
-230
Studies
231
Chemistry
237
(iv) Analogues
8, (Acyclic-7-diene)Fe(CO)3
and ~(7-trimethylenemethane)Fe(CO)3
complexes
238 247
g* q-C&B$"e(cQ)g 10.
(Cyclic-r)-diene)Fe(CO)z_Complexes / @_) Formation QQ
Spectroscopic
(iii) General
and Physico-chemical
Chemistry
254
Studies
1
254 .261 _
198 11.
(~-C+$FeQ-C6H6)
272
l-2.
(py~>p
274
13.
(1'C4H4,Co+C5H9
275
CO ad 14. (7-C5Htz,12
13. Cobalt-carbon 16.
278
[Q-c~H~)~coJ+ Cluster
280
Compounds
284
288
References
1. R.EvIEwS The general
development
has been discussed of titanium,
by Zeppezauerl,
vanadium
di+benzene)
of=-organometallic
and chromium
discussed 2 .
have been
complexes
was also reviewed 3 .
chemistry
of q-cyclopentadienyl,
7Gcomplexes Nobel-prize
4.
Fischer
by Braterman'.
by Knox',
carbonyls,
on the rearrangement
research
work
those
of isotopic
analysis 10 . was discussed
metal
chemistry
metal
complexes
has reviewed
has
the effect
of iron and molybdenum,
of transition
ligands
have been
and in particular
transition
of bicycle k.n.O]
and c-bonded
has been
of transition
Degsnello
of the
has been reviewed5.
complexes
chemistry
especially
of complexes
the
1)-arene and related
review
The organic
been summarized
of 7Gcomplexes
in other sandwich
has discussed
and Wilkinson
substitution inZ-hydrocarbon
possibility
Mawby
7GOrganometallic
included in a more general
spectrometry
Bonding
of hydrocarbon-metal%-complexes
by Bennettbe
cacceptor
and properties
his(r)-cyclopentadienyl),
The7Gorganometallic
winners
The chemistry
of metal
The bonding
and 7-cycloheptatrienyl-q-cyclopentadienyl
compounds
surveyed
chemistry
trienes 9 . metals
The mass
with-aromatic,
has been reviewed. of the elements
The
in the form
199
2. GENERAI;HES&TS Anderson
has used wideline IH NMH spectroscopy to
examine the~structure and bonding in several q-benzene; q-cyclopentadienyl'and 3-cyclooctatetraene sandwich compounds ('2.1; M = V, n_ = 0; M=
Co, n = 1,2;
M = Cr, n = 1;
M = Ni, n = 2;
M = Fe, n = I, 2;
2.2;
_
M = V, Cr, Fe, Co, Ni;
The spectra of the solid complexes were obtained in
2.3).
the temperature range 178-381°K, the second moments of the linewidths were determined and compared with the values using the Van Vleck model. agreement
with very
prillCipa1
molecular symmetry axes.
were
probably
low energy
present
in the q-benzene
compounds
The results were in
barriers
in uranocene
to rotatiori about
(2.3).
(2.1) was
Metal-r%ng
bonding
found to be essentially compounds
(2.2)11.
0 0
32 37.
0
0
u
M
0
0
2.1
2.2 ions
the
Two distinct rotomers
the same as in the 7-cyclopentadienyl
The principal
calculated
formed
2.3
in the mass
spectrometic
frag-
mentation of the 7-cyclopentadienyl complexes (2.2;
M = V,
Cr, Fe and Ni) were confirmed as the molecular ion (7-C5H5)2M+, the 3-cyclopentadienylmetal M+.
The average
ion
dissociation
(7-CsH5)M* energies
and the metal
were
determined
91, 69, 72 and 69 kcal mol-' for the complexes I2 . Cr, Fe and Ni) respectively Referencesp.288
(2.2;
ion as
M = V,
200
Metallation complexes
of the 7-cyclopentadienyl-3-cycloheptadienyl
M = Ti) is lithiated
(2.4; ring
(95%) rather
contrast
metallation
relative
of the vanadium
reactivities
the order M = Ti> used
seven-membered
of these
three
(5%).
ring
and chromium
in the five-membered compounds
A qualitative
V > Cr.
the results 1324.
to rationalize
compound
predominantlyinthe
than in the five-membered
M = V, Cr) occurred
(2.4;
The titanium
(2.4) has been studied.
By
compounds The
ring. decreased
MO approach
in
was
In a definitive
paper,
Q 0
_&I
6
Warren
0
2.4
has discussed
and bis-arene
complexes
configurations
Cmy
elements
state manifolds dependence
and the magnetic
with
the experimental
author
has calculated
static
repulsion
Tanabe-Sugano
moment
results
These
of (7-C5H5>2M,
in the ground
The temperature
auisotropies
for these
in COO*
have also
have been
compared
complexes 15 .
G4 strong-field symmetry
The same
electro-
and evaluated
have been used where
on the
interactionsaud
operators
parameters
the complete
matrices
diagram.
state
Zeeman
The calculated
evaluated.
the ground
for-the
are discussed
Spin-orbital
symmetry.
Possible
field model.
have been calculated.
been
of metallocenes
with &l, a2, _d4 , fi5, s7 and gg
for each &" configuration
of axial
the matrix
behaviour
by use of a ligand
ground-states basis
the magnetic
to
the
deduce
M = V, Cr, Fe, Co, Ni.
202 yield from the oxidation-sensitive complex tricarbonyl(7-cyclohexadienylphenylamine)iron which indicated the mildness of this reaction19.
A US Army report by Rosenblum on
organometallic chemistry covered several related organo-iron chemistry.
areas of
Much of the work in this
report has
already been published by the author in the scientific literature" .
The IR absorption frequencies have been determined for the CO2 groups in a number of mono- and bis-(7=cyclopentadienyl)titanium acetates with increasing numbers of methyl groups on the (q-cyc'lopentadienyl) ligands and with either CF3 or CH3 groups on the acetate ligand21. (3.1;
R = CHMe2,
Treatment of the racemates
CHPh2) with optically active mandelic acid
in benzene led to stereospecific degradation and the isolation of optically active starting material. carried out also with complexes (3.2; C6H3.-2,6-Me2)
bearing
3.1
Teuben
derivatives
R = C6H3.:34fe-6-CRMe2,
cyclopentadienyl
3.2
has investigated
titanocene
a chiral
The reaction was
the thermal
substituent22.
3.3
decomposition
of the
(r)-C5H5)2TiR and their nitrogen
203 complexes
LQ-c~H$~T~R]N~.
The free titanocene derivatives
lost RH by.an intermolecular mechanism:
2(rpC5H&TiR~W
Ti-R
->
%OHgTi
0
d
The compounds showed wide variations in thermal stability dependent on the R group in the sequence: Phe
r=-, R-MeC6H4 < CH2Ph . < "MeC6H4B
The complexes
C6Hs
[(q-C5H5)2TiR]N2 lost nitrogen with the
formation of (7'C5H5)2TiR in the order: R = o_MeC6H4 < C6F5 < CH2Ph < Phm
=-, ~_C6H42~
The green dimeric form of titanocene has been shown by 1% NMR spectroscopy to be a fulvalene dihydrido complex (3.3)24.
4.
(i) Formation (I)-CflHr)Cr(CO "U Rausch has reported an improved synthesis of (q-benzene)-
chromium tricarbonyl.
Equimolar amounts of benzene and
2-picoline containing hexacarbonylchromium were heated under reflux to give a good yield (91%) of the product 25 .
The
reaction of benzocycloheptatriene with chromium carbonyl gave the chromium tricarbonyl complex (4.1) with the six membered The acids PhCH(CHMe2)ring?+bonded to the chromium 26 . CH2CH2C02H and PhCH2CH(CHMe2)CH2C02H were cyclized to give the corresponding tetralones and these-were treated with chromium carbonyl References
p_ 288
to give the complexes (4.2;
R =o<-Me$H,
-2
w$ 4.3
4.2
4.1
chromium tricarbonyl derivatives (4.4;
n = 1 and 2) were
prepared by cyclization of the corresponding propanoic and f o+tetralone ando<-indanone butauoic acids or by reaction 0, with chromium carbonyl28 . The reaction of hexacarbonylchromium with benzocycloheptatriene gave (v-benzocycloheptatriene)chromium tricarbonyl Heating ~-C6Hq[CH(ORt)J2
(4.5j29.
cia 0
.
&,
Ii1
\
w&
0
with chromium carbonyl
/
0 @
_ dr
(CO)
3 4.6
4.5
4.4 gave the complex c4.6;
Rl = R2 = CH(OE~~)] which on hydrolysis
gave the corresponding dialdehyde (4.6; the ether (4.7).
R1 5 R2 = CHO) and
Reaction of the dialdehyde-with ketones gave
the corresponding tropones (4.8)30.
King and Nainan have
205
4.9
4.8
4-7
described the formation of the binuclear anions (4.9;
M = Cr,
W) from sodium tetraphenylborate and chromium or tungsten
hexacarbonyl in boiling diglyme,
The anions were isolated as
their tetramethylammonium salts3?
Neuse and Yannakou have
reported the preparation of chromium tricarbonyl complexes of N-benzylidenear&lLne with metal carbonyl residues attached to either one or the other of the two benzene rings, or to both rings32. syn-(TiDibenaobicyclo[2.2.2]octatriene)tricarbonylchromium (4.11) \vas prepared‘from the arene (4.10) and triacetonitriletricabonylchromium.
Catalytic deuteration
of the complex (4.11) over palladium on charcoal gave predominantly a deuterated product (4.12) with both the deuteriums on the ethane bridge anti to the tricarbonylchromium moiety.
It was thought that this mode of addition occurred
because the tricarbonylchromium moiety served as a blocking group to shield one face of the c&bon
4.19 References p_ 288
->.ll
to carbon double bond33.
4.12
206
Triaqinetricarbonylchromium
was
tre,?ted
with
thiOphC?lle,
t-butylbenzene, phenyltrimethylsilane and iodobenzeno to give the corresponding (T-arene)tricarbonylchromium complexes in yields, as good as or better than, similar reactions with hexacarbonylchromium.
The use of (NH3)3Cr(CO)3 was preferred
in these reactions in that it did not sublime and it VIES more reactive in solution than the hexacarbonyl 34.
(tj-Arene)-
tricarbonylnolybdenum BrXo(CO)- [Ar = PhMe, mesitylene, 5 PhBu, tetralin, (pXe3C)2C6H4, PhO;ie, PhCIkCH2, PhCH2CZ2Cti=CH2, PhC;IgX2CH2Br,
PhCH2CIi20Me,
PhCE2CH2COi3e,
Z,lk,6-i-~e3C6~2CO>~e]
tricarbonyltris(pyridine)nolybdenum
were prepared by treatin
with the aryl compound in ether containing boron trifluoride at 20° 35.
The compounds
benzene, R = Et;
arene
[(q-arene)Xo(PR$d(arene
= mesitylene,
5
R = Xe) were pre>?ared
by reaction of vv -arene)IIo(?-C3H5)Cl~2 with %R3 followed by excess PR3 and NaSH4.
The arene-molybdenum derivatives .:ere
protonated by dilate aqueous acid to give r(rl_arene)~Io(PR3)~H]+ and diprotonated by concentrated acid to &ive [(v-arene)Ko-
4.13
4.14
(ii) Structural an< physico-chemical studies In a theoretical study of benchrotrene, the complete
207
electric carbon This
dipole moment matrix was evaluated on-the metal,
.
centres employing an atomic orbital basis 37.
and oxygen
study was followed by one on (~-c~H~N%)c~(co)~
and
(7-C6H5F)Cr(CO)3 which allowed comparisons to be made of molecular orbitals derived from several approximation methods in common use.
The empirical.method of Basch, Viste and Gray
gave the best values38.
The molecular structure of the benzoic
acid complex (4.13) was determined from three-dimensional X-ray data. p21/s
with
The crystals
w&e
monoclinic,
space
group
unit cell dimensions a = 12.23, b = 7.51, c = 18.1 2
and p= 117.9.
The molecule
(4.13) adopted a conformation
which departed from perfect staggering by about seven degrees 39. Three
dimensional X-ray structure analysis has confirmed the
bis(diphenylarsino)methane adduct of
ctiromi~m
the bridged benchrotrene complex (4.14)40.
hexacarbonyl a6 Meyer has described
the synthesis of several aldehyde, ketone, ketovinyl and hydroalkyl derivatives of benchrotrene by either direct reaction between the ligand and chromium hexacarbonyl or by secondary reactions of substituted benchrotrenes.
The electron with-
drawing character of the chrotium tricarbonyl group was demonstrated by polarography of acylbenchrotrenes, the Hammettsubstituent constant was determined as C=
0.74.. Some aromatic and
organometallic groups were arranged in order of electron withdrawing power;
benchrotrenyl> 2_thienyl>cymantrenyl
)phenyl>2-pyrrolyl>ferroceny141. The rate of hydrogen-deuterium exchange in (CO),PPh3 was directly medium
proportional
at go + 1 to -2.5;
was inverse 4% determined Referencesp_ 288
(7-C6H6)Cr
to the acidity
of the
at 20 -2.5 to -7.1 the proportion
Hydrogen-deuterium exchange rates :rere
for a series
of substituted
arene-chromium
complexes,
'208
(v-RC6H5>Cr(C0>2PPh3(R = H, MeCO, Me02C), (rl-C6H6)Cr(CO)3 and $+Me2NG6H5>Cr(CO)3.
The acetyl and the protonated dimethyl-
amino groups accelerated the rate of exchange43.
The rates
of deuterium and tritium exchange between (?-benaene)dicarbonyl(triphenylphosphine)chromium, labelled in the benzene ligand tithdeuterium
and tritium in CF CO H were determined. No 3 2 isotope effect wss observed and it was suggested that the rate determining step in the exchange might be the transfer of H+ from chromium to the benzene ligand44.
Substituent effects.
in benchrotrene derivates have been studied. by measurement of rates of cleavage for C-MR
3
groups bound to theq-benzene
The triethylgermane (4.15;
ligand.
X = H) was cleaved by
aqueous-methanolic alkali sixteen times faster than the free ligand which gave a value for the Cr(COj3 substituent constant 6=
+0.84.
(4.15;
The relative rates of cleavage fck the complexes
X = m-CF3, @?l,
g- and R-OMe, o- and S-Me, H) were
found to correlate well with the relative rates for the free ligands although the substituents (X) had a smaller effect in the complexes (4.15) than in the uncomplexed arenes.
Similar
effects were observed in the basic cleavage of the aryl-SiMe
3
bond in a series of six silylbenchrotrene compounds (4.16; X = m-Cl, _- and &-OMe, ;- and &-Me, H).
The 6- constant
was determined as +l.l2 for the Cr(C0) group in the silicon. 3 complex (4.17)45.
4.15
4.16
4.17
209
Ceccon and Catelani have compared the rates and products of elimination from the substituted benchrotrenes (4.18; Rl = H, N02, R2 = H, Me, X = Br, OTs), with those obtained from the free arenes.
The eliminations were carried out
with ethoxide in ethanol or t-butoxide in t-butanol,
Higher
rates of reaction were observed for the complexes than for the uncomplexed arenes.
The percentage of olefin in the
product mixture when substitution competed with.elimination was greater for the compleired arene while the proportions of the olefin products were independent of complexation 46.
In a related study, the second-order elimination from the complexes (4.18;
R1 = H, R2 = Me, X = Br, OTs and 4.19)
has been compared quantitatively with the same reaction in the free ligands.
The reactions were induced b-y either
tetrabutylammonium chloride or bromide in acetone.
The rate
of dehydrochlorination of 1-phenyl-1-chloropropane wae almost unaffected when it was complexed as (4.19) but the rate and olefin yield from the 1-phenyl-2-propyl derivatives was decreased on formation of the complexes (4.18).
An Ez!c
transition state for the reaction was preferred over the alternative R2H transition state 47. The kinetics of decomposition of several ('I-arene)chromium-tricarbonyl and References p_ 288
-dicarbonyltriphenylphosphine
210
complexes
was-studied
spectrophotometrically
The complexes
conditions. decomposed
faster
decomposed
to give benzene
rapid-exchange
between
releasing) terms
the conformers
(4.20;
with a decrease
of an increased
The opposite
(R is electron
rotation
shift
for (4.20;
to rotatiM
xH2,
:C=CH2,
kcal
nol'l
at 14-22O
had energy
barriers
respectively.
2, 4
in
(4.21).
c4.20;
R =
tricarbodyl
EIindered compounds
The energy
in the complexes
barriers (4.22;
4.21
4.20
X =
rings
atoms
R = COMeI
(4.20)4g.
by 'H NMR spectroscopy.
of the uncomplexed
by variable
and this was attributed
conformer
in (v-diarylmethane)chromium
for
(R is electron
from conformer
occurred
The
was interpreted
For the complex
of a single
has been studied
118’
in temperature
withdrawing).
to the existence
for carbon
R = Me, Et, OMe)
was observed
C(Me13] no significant
48 .
was studied
shift
contribution
behaviour
Benchrotrene
(4.20 and 4.21)
complexes
An upfield
and 6 in the complexes
compounds.
and- hexacarbonylchromium
benchrotrene
13C ?&R.
first order
triphenylphosphine
than the tricarbonyl
some substituted temperature
containing
under
>CHOH) while
fell in the range the complexes
of 19.4 and The
13.9-14.3
(4.23;
R = H, Me)
19.6 kcal mol-' at 115 and
high barriers
for the ketones
(4.23)
.
211 were ascribed to stabilisation of the ground-state conformations by carbonyl-uncomplexed ring.conjugation5'.
4.22
Bodner and Todd
4.23
4.24
have used Fourier-transform 13 C NMR spectroscopy to study substituent benzene6
effects
were
benchrotrene
when benzene
complexed derivatives
C02Me, NH2, NMe2).
with
and eight substituted
chromium
(4.24;
carbonyl
to give
the
R = F, Cl, Me, OMe, OHun,
No significant
change
in the transmission
of resonance substituent effects was observed between the free and complexed ligands.
The chromium tricerbonyl residue
was effective in withdrawing electron density from the &skeleton
of the erene ring51.
Complete assignments of the vibrational spectra of the benchrotrenes (4.24;
R = NH2, OMe, C02Me) have been made
on the basis of Raman polarization_ results.
The need to
use full factor-group analysis iS emphasised and attention is called to the failure of the 'local' symmetry concept which has been used previously 52.
A single-crystal Raman
study was made of the vibrations of-the tricarbonylchromium unit in benchrotrene and tricarbonyl(l,g-dimethylbenzene)chromium.
In the 2000 cm"
wa6 appropriate.
were interpreteds3.
region a factor group analysis
Also, low frequency bands, 400-700 cm-l,
.
-212
The chemical ionization mass spectra for the (T-arene)chromium tricarbonyls (4.24i
R = H, Me, F, Cl9 GO,Ple> have
been recorded and compared with the spectrum of q-cycloheptatriene)chromium tricarbonyl..
In each case the spectra
were interpreted in terms of protonation at the metal atom. In the case-of di(q-benzene)chromium the most abundant ion was the molecular ion formed by loss of a hydrogen atom from the protonated complex54,
The dissociation and fragmentation
of six alkyl- and halogeno-benchrotrenes has been examined by mass spectrometry,
Appearance potentials were measured and
dissociation energies obtained for the neutral molecular and the major fragment ions 55.
The mass spectra of (v-acetanilide)-
tricarbonylchromium and the 2,4- and 2,6-dimethyl analogues indicated that ketene elimination from the ion ~C6R5RHCOCH3)C~+ . occurred via a six membered transition state, Scheme 4.1 5%
Scheme 4.1
In the mass spectrometer (y-methyjbenzoate)tricarbonylchromium underwent secondary electron capture to give a molecular ion which suffered decarbonylation and further loss of three CO groups.
Cr- ions were also identified in the 7OeV negative
ion mass spectrum of this compound 57.
The use of mass
spectroscopy for the analysis of mixtures of (q-benzene)tricarbonylchromium complexes was investigated,
Intense
213
peaks were obtained for the molecular ions [(7-CgH5X)Cr(CO>d+ (X = 11,Me,.Et,
F and Cl) and r(t?-C6H5X)Cr]+.
[(~-c~H~x)c~co]+B~-c~H~x)c~(co)~]+ useful
The ions
and (c~H~x)+ were
also
in the identification of the (q-benzene)tricarbonyl-
chromium derivativess8.
(iii) General Chemistry. Benchrotrene was mercurated with mercury (II) acetate to give the derivative (4.25;
R = H) in 29% yield.
Triethyl-
silylbenchrotrene was metallated in the same way to form the disubstituted compound (4.25;
R = SiRt3)59.
The quantum
yield for the photochemical decomposition of benchrotrene . in cyclohexane was found to be proportional to the rate constant for decomposition and was inversely related to the intensity of the light used.
A
complex mechanism of
decomposition was indicated with three competing reactions 60 . Jaouen and Dabard have cyclized the butyric acid (4.26).with polyphosphoric acid to give a mixture of the endo-cyclopentenone (4.27),
52%
and the e-isomer
(_4.28),48%.
When either the
endo- or the exo-isomer was heated with sodium methoxide then an equilibrium mixture of the two isomers was obtained containing the same proportions as were
formed in the initial cyclization,
The equilibration presumably proceeded through the enol form (4.29) of the cyclopentenones.
Cyclization of the butyric acid (4.30) also gave a.pair of isomeric products 61 o
R\
P0
HgOAc
(%, 4.25
4.26
4.27
4i28
4.30
1.29
The reac_tion of methylmagnesium iodide with the dialdehyde (4.6; R1 = R2 = CHO) gave a mixture of two meso, pseudoasymmetric glycols and one racemic glycol
r4.6; R1 = Rz = CH(OH)Me]. ligands
Photochemical removal of the
gave two diastereoisomeric alcohols (4.31).
Oxidation of the alcohol_ c4.6; R1 = CH20H, R2 = CH(OH)Me] gave the cyclic hemiacetal (4.3Z; X = H, R = OH) and the phthalide (4.32;. X = 0, R = H)62.
The Penchrotrene monomer
CH(OH)Xe
4.32
4.31
(4.33) was prepared from (q-2-phenyIethanol)chromium tricarbonyl and acryloyl chloride in benzene.
Approximate reactivity
ratios were obtained for the copolymerizatfon of the monomer (4.33)mwith styrene, methyl acrylate, acrylonitrile and 2-phenylethylacrylate in ethyl acetate with azobisisobutyronitrile as the initiator. (4.34;
High yields of the copolymers
R = Ph, C02Me, CN, C02CH2CH2Ph) were obtained at 70°
and
all exhibited
The
organometallic
bimodal
molecular
residues
weight
decomposed
distributions.
in sunlight
and on W
irradiation in air or under nitrogen with the.initial-formation of Cr203 63 . The symmetrical benchrotrenyl mercury compounds
(~HCi12cHRcH2)n
Q-
cHpi20coH=cH2
CH2CH,0C0
0
4.33 R = H, Me, OMe, NMe2)
(4.35;
aluminium
hydride
to give
Cleavage
cleaqed
the substituted
with iodine
(4.36;
at low temperature
R? = H, Me, OMe, NMe2,
with
lithium
benchrotrenes
(fj-Chlorobenzene)chromium the anion
in ether
activating References p-
tricarbonyl
of isobutyronitrile
(4.39;
complex
288
gave
the iodo-benchro-
R2 = I> 64.
4-36
4.35
iodine
were
Rl = H, Me, OMe, Nt4e2, R2 = H) in good yield.
(4.36;
trenes
4.34
(4.37)
treated
to give the chromium
R = CMe,CIJ) which was readily to give phenylisobutyronitrile.
effect
was
of the chromium
tricarbonyl
with
tricarbonyl
cleaved
with
The large was apparent
-
216
-in that the reaction wae complete within 20h whilst no reaction occurred with uncompl&xed chlorobenzene over a Several other anions were-used successfully
similar period.
in this reactidn, however those generated~from 1;3-dithisne, 2-methyl-1,3-dithisne, tert-butyl acetate, acetophenone, 5,6-dihydro-2,4,4,6-tetramethyl-4EJ-l,3-oxazine and acetonitrile fai.led63.
The mechanism of the reaction of carbauions with
(v-chlorobenzene)chromium tricarbonyl (4.37) was investigated. It was suggested that attack by the carbanion occurred to form a (rj-alkylcyclohexadienyl)chromium tricarbonyl anion (4.38) followed by irreversible loss of halide anion to give the When an electrophile was added to the reaction
product (4.39).
system of-(4.37) and the anion, followed immediately by addition chlorobenzene,
of iodine, the following products were isolated;
phenylisobutyronitrile, g- and g-chlorc(2-cyano-2-propyl)benzene and a series of dihydro analogues of these last t7;o products66,
+
?&-
‘$If
0
+
cl-
Cr (cJO13
4.37
4.38
4.39
(7-Mesitylene)chromium tricarbonyl and other (q-arene)chromium or molybdenum tricarbonyls have found application as catalysts for the polymerization of phenylacetylene 6? (q-Phenanthrene)chromium tricarbonyl-has been.used to catalyse the selective hydrogenation of a propellatetraene to-the
217
corresponding propelladiene 6% .
Phenylacetylene-was polymerized
rapidly and quantitatively in the presence of (q-toluene)molybdenum tricarbonyl to give linear polymers with molecular weights up to 12,000.
The polymerization proceeded'via a.
ladder polymer intermediate which wae isolated when (7-mesitylene)chromium tricarbonyl was used a6 the catalyst. The ladder polymer rapidly gave linear polyphenylacetylene in the presence of (tj-tolueneholybdenum tricarbonyl and this reaction was thought to proceed via a free-radical mechanism 69 .
(iv) Analogues Jaouen and Dabard have ccnverted monosubstituted benchrotrenes into chiral complexes by replacement-of carbonyl groups by other ligands.
Thus (v-methylbenzoate)chromium tricarbonyl
was treated irith cyclooctene to form the derivative (4.40; L = C8H14) and this intermediate wa6 stirred with carbon disulphide and triphenylphosphine to give the thiocarbonyl complex (4.40;
L = CS).
Irradiation of the thiocarbonyl
complex with triethyl phosphite led to the chiral phosphite Several disubstituted benchrotrene derivative6
(4.41). c4.42;
X = H, But, Me;
PPh3] were described?',
R = H, Me, menthyl;
I, = CO, P(OR)3,
The photosubstitution of a carbonyl
group in (q-ArH)Cr(CO)3 by N-phenylmaleimide (NPhMI) gave References p_ 288
_
Irradiation of complexes of this'type
Q-ArE)Cr(CO)2(NPhMI).
in the presence of a phosphite gave the chromium complexes (4.43
and 4.44).
These compounds are the -first neutral
asymmetric (90benzene)chromium (0) complexes with the metal atom as the
chiral centre,
The vinylic protons of the
N-phenylmaleimide ligand were diastereotopic and displayed Photolysis of qa temperature dependant 1H NMR spectrum7'.
Q 0
0
Cr C0.P(OMe)3.
4.43
0
iiPh
CO.P(OPh 4 -44
c
0
0
-LCr(CO)3[L = hexamethylbenxene, mesitylene, E-RC6H4Me, (R = Me2N, Me, MeO, F and CO2Me), C6H6, and e-(Me02C)2C6H41 in the presence of 2,3-diazobicyclo[2.2.1~hept-2-ene gave I;I-LCr(C0)2Ll.
(L1)
The ligand Ll was coordinated to
chromiu1r through the lone pair of electrons of one of the nitrogen atoms of the N=M double bond72.
Connelly and
Demedowicz have displaced carbonyl from (7-C6Me6)Cr(CO)3 using the diazonium salts (H-.NCgH4N2>X (H = li,X = FFg; R = OWe and NO 2, X = BF4> to afford the complexes (7'C6Me6)Cr(C0)2(R-RC iIN )fX-wbich were cla?i_ned to be the first 642 examples of arylazochromium derivatives. Treatment of these derivatives :fith sodium borohydride gave the corresponding neutral cyclohexaciienyl complexes (7-r,6~~e6H)Cr(C0)2(E_IiC6H4~i~), The reaction of (r;i-C6ife6)Cr(CO)2PPhg with (H-RQH~N~)+
gave
the paramagnotic cation [r)-C6Me6Cr(CO)2(PPh3)]+ where the diazcnium salt had behaved as an oxidizing agent.
219
(r7-C6Pie6-Ploo(CO)3
was treated also with (o-RC6H4N2)+ to give
complexes that were apparently analogous to~the chromium species but no stable products were isolated 73.
The reaction of
(v-C6Xe6_nHn)Cr(CO)2PhCECPtl,.n = O-and 1, with either I~OP&'6 or AgPF6 gave the air stable salts [(7-C6Ne6;nHn)Cr(CO)2 (PhCZCPh)]pF6.
The carbonyl stretching frequencies for the
cations were 100-15O.cm -' figher than those of the neutral ccmpounds,
Cyclic voltammetry showed that the neutral acetylene
complexes underwent a reversible one-electron oxidation 74. 6-Methyl-2&thiopyra:
iVas heated with (XeCi1')3Gr(C0)3 in
dibutyl ether to form the benchrotrene analogue (4.45)
in which
sulphur coordinates to the m_etal with nonbonding as well as olefinic electrons.
The physical properties of the complex
were compared with those of (t'j-thiophen)ciironium tricarbonyl and the corresponding (q-1,2-dihydropyridine)chcomiun complex75. 3iophen)cbrcmhun tricarbonyl complexes was A series of (7-t.
4045
Scheme 4.2 prepared by reaction of the appropriate heterocycle with (IqeCN)3Cr(CO)3.
The yields
in
these eeactions were higher
than in preparations utilizing Cr(CO)6. Referencesp.288
The separation
and decomposition of the thiophene complexes was studied by gas-liquid chromatography.
Treatment of the complexes with
benzene resulted in ligand exchange (Scheme-4.Z)76.
The
1HLiMR spectra of the q-thiophene complexes were analysed7'. The treatment of (P7-Me3B3N3Meg)Cr(CO)3 with Me3B3N3H3 brought ‘about ligand exchange to give (v-Me3B3N3H3)Cr(CO)378.
scotti
and Werner have attacked substituted borazines with Cr(C0)3(MeCN)3_to give the chromium complexes (7-R13B3N3R23)Cr(CO)3 1 = Pr, R2 = Me; Rl = Me, R2 = Fr; R1 = iso-Pr, R 2 = Me; 2 = Me, R2 These compounds were more labile than the isomeric complex (7-Et3B3N3Et3)Cr(CO)g which was prepared from (7-iX3B3N3Meg)Cr(CO)3 by ring'ligand exchange 79.
The direct synthesis of bis(q-m-diisopropylbenzene)chromium, bis(T-cumenelchromium and (v-biphenyl)(y-g- dipropylbenzene)ChrOmiUm
from
C~0Kh.m
and the arenes has been reported 80 o
Chromium atoms were cocondensed with benzene in an argon matrix, on a caesium iodide window at 14OK, to give di(y-benzene)chromiup which was characterized by infrared spectroscopy 81 . Nickel atoms were treated with hexafluorobenzene to give a highly reactive and explosive complex.
In a similar manner
hexafluorobenzene and benzene were allowed to react with chromium to give presumably bis(hexafluorobenzene)- and di(v-benzene)chromium respectively 82 . The formation of bis(q-arene)metal complexes has been achieved by condensation of metal atoms obtained by resistive heating with the arene at -196'.
Arenes used were benzene, toluene, xylene, anisole
and fluorobenzene and these were condensed with molybdenum and fungsten83.
Bis(v-arene)molybdenum complexes have been
221 separated from mixtures and purified by molecular~distillation 84 . A series of bis( -fluorobenzene)chromium complexes-(q-C6HkFX)#r
7 (X = H, F, Cl, CH3, CF3) were prepared by cocondensing chromium
atoms and fluoroarenes,
The lg F NMR spectra of these complexes
suggested that the overall electron-withdrawing effect of a W-bonded
chromium atom on each ring was similar~to that Of
four ring fluorine substituents 8% The X-ray photoelectron (ESCA) spectra Of fourteen bis(7-arene) and (y-arene)tricarbonyl complexes of Cr, pin and The binding energies
Fe were measured in the solid state. were interpreted with the aid of &
initio SCF MO calculations
for (t7-C6H6)Cr(CO)3 and (3-C6H6)2Cr and semi-empirical MO calculations on most of the other compounds.
In neutral
bis(7-erene)metal complexes the arene ring carried a small negative charge and the electron density on the ring was higher than in the comparable (v-arene)tricarbonyl complex 86 ( Simple mass spectra were obtained, for a series of bis(7-arene)chromium and -molybdenum complexes, at 60o for the chromium compounds and at 100° for the molybdenum compounds, by the use of a field-ionization source.
The ions (5.1;
i+ =
Cr, .pIo)
were formed preferentially and the method was suitable for qualitative and quantitative analysis,
Mass spectrometry
wvith field ionization was also used for studying the thermal - 87. decomposition of these compounds
The dependence of the
hyperfine structure of EPH signals of bis(r/-arene)chromium compounds [e.g. (7-PhH)$r+,
(q-PhMe)$r+,
(I?-PhPh)#r*] on
temperature (-160~-+70~), viscosity, solvent and magnetic field was studied.
The line width temperature dependence was
explained by the relaxation mechanisms: anisotropic Zeeman interaction; References
p_ 388
when o?r >I_, an
vrhen oTt(
1, a modulation
of spin reversalinteraction 88 . ~bisq-arene)chromium.iodides
A synthetic mixture of
was resolved by partition liquid
.chromatography and the chromium content in each fraction was determined by atomic absorption spectrometry 89 .
+
Q 01
0’
0
O-
0
M
Cr
6 0
The kinetics
0
R
& t
I-
0
6-R
5.1
5.2
5.3
of hydrogen-deuterium exchange for the R-= H, Ze, Zt) in L;t@D-EtONa and for the
complexes (5.2; salt (5.3;
Q-
+
R = 11,r.le) in D20-KOD were studied*.
In both
reactions deuteriun e!itered both the aromatic nucleus and the
side chain".
The kinetics for the thermal decomposition
of the diarenc complex (~-PhEt)2Cr was correlated with its field mass spectrum 91.
The saturated vapour pressures for
a series of bis(q-arene)molybdenun complexes were determined and the-heats of evaporation ?lr-recalculated-92 _ The saturated vapour pressures of the benzene complexes (q-Ph!'>2Cr, (7-P&(9-PhEt)Cr
9 (7-PhLt)C7-C6H4Et2)Cr alid (7-C6H3Me3)2 Cr
yiere deternined at 20-110' and the heats of evaporation were 3easuredg3.
z Rxwessions
have been derived to correlate the
physicochemical properties, such as densit;::and vapour pressure, of bFs(q-arene)metal complexes.
The arene ligands :fere benzene
and substituted benzenes and the metals were chroaiu:l, Zmolybdenum and tungsteng4. Bis(r)-bcnzene)c':*roniu!~ ;:as Xeteroann-ularly dilithiated with
223
a mixture of butyllit'hium and TiGDA in cyclohexane at 70'. The lit:hio intermediate vfas stirred with diphenylchlorophosphine to give the diphosphine (5-4) which was coirverted to the dimethiodideg5.
Xixed sandwich complexes of c'hromium have been + 2 AlR2C12
PPh2 Cr
5.4
5.5
formed by direct reaction between chromium salts and acetylenes. Treatment of 2-butyne with chromium (III) chloride and tri. alkylaluminiuts gave the q-benzene cation (5.5; R1 = He, R2 = He, Et, Pr>.
The cation was reduced with lithium
aluminium hydride to the neutral sandwich compound (5.6; R=Me).
. Replacement of 2-butyne with 2-hexqne in the same
reaction gave the y-benzene cation (5.5;
R1 = a,
Rz = LXe,
Et, Pr) which on reduction formed the T-benzene complex (5.6;
R = 53~).
It was suggested that the polyalkylbenzene
ligands vere formed by cyclotrimerization of the acetylenes while the cyclopentadienyl groups arose by cleavage of the acetylenes at the triple bondg6.
Eis(t)-diphenyljchromium
was oxidized with a stream of oxygen in the presence of l,+diphenyltriazine
to give the salt (5.7) which was isolated
as the sesquihydrateg7.
References
p. 288
BisOpethylbenzene)chromium
was
224
5.7
5.6 pyrolysed
at 350-450'
for 10h to give methane,
carbons and chromium as the main products
C2-C4
together
hydro-
with
mink
amounts of hydrogen, toluene and ethylmethylbenzeneg8.
6.
[07-C7H7)Cr(CO) dc, AII improved
(f7-C7H~,)Cr(CO)3
synthesis
04 = Cr, MO) was reported i-C$i5MgEr.
The reactants
TiiF-diethylether
0
at -20 .
for the compounds
(v-C5H5> (r?-C7H7)M
from 19iC13.3THF, C7Ha, were mixed
together
C5H6 and in
The product was purified by
sublimation and subsequent recrystallization.
The synthesis
and properties of (7-C5H5)(T-C7H7):4, (M = !&r,Nb) were reportedgg.
Green and co-workers have reported a general
route for preparing non-carbonyl cycloheptatrienyl molybdenum compounds via the facile displacement of the arene ligand from the complexes
[Q-C75)(7-arene)
Xo]+PF6- as shown in
Scheme 6.11"'. The crystal structure of 1,3,3,5-tetramethyl-6-(1',2*naphtho)bicyclo[3,2,l]octenechromium determined by X-ray analysis.
(0) tricarbonyl was
The crystal data was as
follovEi: space group s2/~, a = 19.66, b f 14.35, c = 16.442, = 120,1°, z = 8.
The cyclohexane ring was distorted from
the normal chair form due to the steric interaction of an
:ioPPh_(acac)
Scheme
6.1
0 naphthalene moiety and the strain axial methyl group with th, of fusion through a five-membered ring to the naphthalene moiety.
The chromium atom was complexed to the ring of the
naphthalene that was fused to the aliphatic part of the moleculel~l.
X-ray photoelectron spectra (ESCA) on
$'-C5h5)(7-C7h7)M, (M = Ti, V, Cr) and some related compounds showed that the oxidation state of the metal increased in the sequence Cr< V< Ti.
This resulted in an-increased electron
density on the ligancis in the same sequence.
In the Cr
compound the cyclopentadienyl ring was more negative than the cycloheptatrienyl ring; References p. 288
for the V compound about equal negative
226
charges were found on the two rings;
while for the Ti compound
the'highest negative charge was found on the-seven membered ring102; 13 C and IH Nk3R spectra of the compounds (7-C5H5)(q-C7H7)X, (W = Ti, Zr; &lo, Cr) were recorded. the chromium compound the 13C reson&e
For
of the ~-C,-& ring
was at lower field than that for the 7-G5H5 ring,
whilst
molybdenum compound the two signals were close together.
fOl?
the
r
It was concluded that the q-CsH5 ring was more negatively charged than-the q-L/$ ring in the chromium compound. 1H NMR spectra indicated hindered rotation of the rings in The mechanism of the chromium and molybdenum compounds 103. fluxional rearrangement in (7-cyclooctatetraene)trice.rbonylmolybdenum was investigated using 13C MR
spectroscopy.
The results ruled out a 1,2 shift and it was proposed that . the rearrangement process involved a symmetrical "piano stool" intermediate (6,1), Scheme 6.2, with the metal atom lying over the centre of a flat octagonally symmetric C8H8 ring 104 .
(co) - x0-
5
;0.--_
I~~o(co)3 \ ..-I\
,-
\
:
\-__* I
0
\
6.1
“__
;
227
The fluxional behaviour of the chromium tricarbonyl derivative (6.2) was reexamined with 13C NXR and it was process occurred.-- For the chromium
proved that a 1,2&hift
tricarbonyl derivative (6-s), 13C NMR showed that 1,2-shifts were not the pathway and that only 1,3-shifts or a process 'resulting in random shifts were admissible 105 _
$I
Q
6.2
.
6.3
The reaction of (v-cgcloheptatriene)metal tricarbonyl (where metal = chromium, molybdenum or tungsten) with acetonit-rile obeyed third-order kinetics.
The reaction was
interpreted in terms of pre-equilibrium association between then-complex
and acetonitrile which was followed by rate-
determining addition of a further molecule of acetonitrile. The ease of displacement of the ligand decreased in the order i+Io>X>Cr. the
COni,oleX
Displacement of the aromatic ligand from
(7-C6H3Me3)i”iO(CO)3
by acetonitrile _ followed
second-order kinetics and led to the following order of displacement of ligands (L) from the complexes LMo(CO)~~+ where n = O,l;
7-C71i8>'7-C6~3"e9>3-C7H7106~
of D'7-c7H7)Mo(C0)~BF4
with triphenylphosphine gave
~~-C7H$';10(CO)2PPh~BF4
nhich was reduced with sodium
borohydride to g~ve'(~-C7H~)&~o(C0)2PPh3107. complexes of
chromiun
The reaction
(6.6; R1 = Ph, He, H;
Yepta-fulvene R2 = Ph, Me, H)
have been obtained from the -l-substituted cycloheptatriene References
p_ 288
compounds (6,4).by hydride ion abstraction with triphenylmethyl ~fluoroborate to form the tropylium salts (6.5) which were treated pith 1,8-bis(dimethylamido)n~phthalene,
a strong
anon-nucleophilic base, to abstract a proton and give the These compounds resembled free heptafulvenes
products (6.6).
in their reactivity towards electrophiles with exclusive attack at the exocyclic double bond 108.
6-4
7. 07-C5H+n(CO)
6.5
y
6.6
(i) Format-
C?-(Trior~anosilyl)cyclopentadienyl]tricarbonyLmanganese compounds were prepared by treating a (triorganosilyl)cyclopentadiene with an alkali metal, heating the resultant metal derivative with manganese (II) salts and treating the intermediate bis(7 -cyclopentadienyl)manganese with carbon monoxide at lOO-200' and 50-200 atmospheres 109_ The dioxolanylcymantrene
(7.1) was _urepared by condensation of
acetylcymantrene with epichlorhydrin in the presence of tin (IV) chloride using carbon tetrachloride as solveni?lO. Bis(cymantreny1) copper silver (7.2) was formed by treatment of cymantrenylsilver vlith copper (I) iodide in benzene. The ccmplex (7.2) -.vasconverted to benzoylcymantrene with benzoylchloride, to~phenylcymantrene with iodobenzene and to
229
ferrocenylcymantrene (7;3) with ferrocenylbromide, . -xields~were in the range 70-i33YP1.
King and Ackermann have investigated
@Ox 0
Cl
XIl
WO13 7.2
7.1
7.3
the reactions of olefins and acetylene with [HMn(CO)4]3 under mild conditions.
Dienylmanganese tricarbonyl compounds
(7.4) were formed in several cases, thus 1,3-cyclohexadiene give the cyclohexadienyl compound (7.4; heptadienyl compound (7.4;
(7.4;
n = 3j
The cyclo-
n = 2) was formed from both
cycloheptatriene and 1,3-cycloheptadiene. with lJ,+cyclooctatriene
n = 1).
The same reaction
gave the cyclooctadienyl compound
together with other manganese complexes.
The
dienyl complex (7.5).was formed in addition to a fluxional dimanganese complex when cyclooctatetraene was the reactant. Xhen
dimethylaminofulvene
derivative (7.6)
7.4
R&?rences p. 288
was
used
then the cymantrene
was obtained112.
7.6
2io ;Sii> Saectrosconic and-Physico-chemical Studies ..&mantrene was irradiated tiith-X-rays.ar electrons -and the free radicals formed were exanined'by
EPR
spectroscopy.
The-anisotropic spectrum of the final, stable paramagnetic species was compared with the theoretical model
based
on-the
crystal field approximation modified for covalency effects 113 . The frequencies of-the metal-cyclopentadienyl and metal-carbonyl stretching modes in $J-cyclopentadienyl)tricarbonyl-manganese and -rhenium were compared,
The frequencies of the manganese-
-ring stretching vibrations increased whilst those of manganese-carbonyl decreased with an increase in%-acceptor properties of the substituent H in the ring.
The frequency
of the rhenium-ring stretching vibrations was independent of the substituent R.
These differences shoned that the
dative d?t(metal)-p&CO) was more important in the formation of the metal-ring bond in (r)-RC5H$!-ln(CO>3than in the corresponding rhenium compounhl14.
Parker has obtained the IR and laser
Raman spectra of cymantrene and (~-C5D5>Iti(CO)3.
The solution
spectra may be assigned approximately on the basis of C _5V 'local' symmetry but this approach cannot be used for the assignment of the solid state spectra 115. the manganese-q-cyclopentadienyl
The protonation of
complexes (7.7 and
studied with 13C and 31P NMH techniques,
7.8) was
The complexes were
subject to rapid reversible protonation at the metal atom in the presence of trifluoroacetic acid.
The protonation was
governed by the basicity of the manganese atom which depended on the number and nature of the phosphine ligands.
The
basicity of the diphosphine complexes (7.8) was higher than that
of the
monophosphine
complexes
(7.7)
and the alkyl-
phosphines were better electron donors than triphenylphosphine 116.
izn C0.L 7.7
L = P(C&&,
P(i-C3H$3, PPh
7.8
IL*= PPh5 Lz = Ph2PCHZCH2PPh2,
P(cH2Ph+
Ph2PCH2CE2CH2PPh2
3
The IH NMH spectra of cymantrene and fifteen monosubstituted cymantrenes have been compared with the spectra of the corresponding rhenium compounds. . In each case the electron density on the 3-cyclopentadienyl group was higher in the cymantrene compounds than in their rhenium analogues 117 o (iii) General Chemistry Treatment of the (v-cyclopentadienyl)manganese complexes (7.9) with hydrogen borofluoride in tetrahydrofuran gave the gold complexes (T-10;
R = CO, PPh3)l18. AuPPh_
5
Tricarbonyl(y-cyclo+
AuPPh_ 5 BFL&-Ilrl
(=$R 7.9
7.10
pentadienyl)manganese was treated with Et2NPC12 to give
&CO)3Mn(7-C5H4)]3P= C13PS and -methyl iodide
Treatment of this phosphine with Hz02, gave [(CO)3Mn(~-C5H4)1~P0, KCO)3-
413
Mn(7-Cg H ) PS and [(CO)3Mn(7-C5H4f13$MeI- respectivelyllg. The photochemical reactions of (~-C5H5)~Mn(CO>3 and (triphos) gave (r)-C5H5)~In(CO),(CS) with (Ph_,PCH2CH2)21?'Ph (7-C5H5)Mn(CO)(triphos), as two isomers (7.11
and 7.12) and
232
(7-C5H5 )Mn(CS)(triphos) respectively,
as two isomers, (7.11 and 7.12)
The presence of one uncoordinated phosphorus
atom in the complexes was confirmed by their-reactions with Cr(CO).$THF) and (7-C5H5)Mn(CO)3 to give the bimetallic species, (7'CgH5)(CO)Mn(triphos)Cr(CC)5, (7-CgH5)(CS)f4n(triphos) Cr(CO)5, (7-C5H,$CO)Hn(triphos)Mn(C0)2~7-C5H5)
and (745H5)
(CS)~Nn(triphos)Mn(C0)2(rl-C5H5). The reaction of (q-C5H5_) Mn(CO),CS with Ph2PCH2CH2PPh2 gave (7-C5H5)YZ(CS)Ph2PCH2CH2PPh2. The absence of any CS substitution by the phosphorus ligands demonstrated the stronger metal-carbon bonding in metal thiocarbonyls as compared to metal carbonyls12',
L =
L 7.11.
co,
GS
R = CiiCB PPh 22 2
7.12
(7-Methylcyclopentadienyl)tricarbonylmanganese
was fed
orally to rats and it caused histopathological changes in the lungs, liver and kidney. to the dose,
The degree of severity vias related
Manganese concentrations in the tissues of the
animals given 15-150 m&/kg was high,.those that survived the treatment had normal manganese levels fourteen days after the complex had been administered. manganese metabolism
The results indicated that
was homeostatically
controlled
and
that the manganese was transported in the tissues as a netabolite of the original complex 121 . The thermal stability of siloxanes containing tricarbonyl(7-cyclopentadienyl)manganese
233
was
reviewedl=,
Acetylcymantrene was converted to the ketal
(7.15) by treatment with epichlorohydrin and tin (IV) chloride in carbon tetrachloride 123.Silvercymantrene was treated with trinitrobenzene and tropyfium tetrafluoroborate to give the
.
anion (7.14) which was oxidized to 1(2,4,6_trinitrophenyl)cymantrene124.
The cymantrene
gold complex (7.15;
7-14
7.13
X = CO)
7.15
was irradiated with triphcnylphosphine ;inbenzene to give the cymantrene analogue (7.15;
X = PPh5).
When an excess of
triphenylphosphine was used in the reaction then gold-carbon cleavage was observed rather than replacement of a second car-bony1 group by triphenylphosphine-125a The effect of manganese based additives, e.g. (7-methylcyclopentadienyl)manganese tricarbonyl on the mass, size distribution and the chemical composition of particulate emissions from gas turbine combustors. was investigated, The presence of large amounts of Q-methylcyclopentadienyl)manganese tricarbonyl increased
the mass of the emissions with
the manganese being discharged as MnO 126 .
Lithiocymantrene
was treated with triphenylsilicon-, triphenylgermanium-, triphenyltin- and triphenylead-chloride to give the cymantrenes
(7.16; M =.Si, Ge, Sn, Pb). in the tin compound (7.16; References
p. 288
The tin-cyclopentadienyl bond H = Sn) was cleaved with dry HCl
~&fetalcarbonyls and orginonetallic compounds, including methylcymantrene, have been incorporated into polymeric an&o&es
of benzyldiphenylphosphine.
The
polymer-bound complexes have been evaluated es hydroformylation and oiefin isomerization catalysts 128_
Xn (CO) 3
7.16 ET-MeC5H4)fi(C0)2NOJ+
i4ll
(CO)2itO
7.17 PF6- was treated with (g)-(+)-
-HePhChN~4e(PPh2) (ligand L) in acetone in the absence of air to give the pair of diastereoisomers of the tetrahedrally The isomers
-coordinated complex
~~-X~C~H~)X~(CO)(NO)LJ+PF~-. were separated by fractional crystallization 129 .
Details
have been given for the preparation of C('/-C5'15)I.I"(CO)2NO]PF6 from (7-C5II5)Mn(CO)3 and ivOPF6130 a (7.17;
The cymantrene analogues
R = H, 14e) gave the carboxamides (7.18;
R1 = H, Me,
R2 = alkyl, aryl) on treatment with primary amines in ether 131 . -AeC H )PIn(C0)2THFwith an excess of Q?54 O<-diazodeoxybenzoin gave the phenylcarbene complex 7.19?32. Reaction of
7.18
7.19
7.20
Treatment
‘of c$ti&trene
the mixed
complexes
writh $ubstitut&d
of the isoelectronic
(~-c~H~)M~(c~)~cH,=cH,
indicated
that
dependence
the ethylene
motion
kcal/mole
ligand
reported133. dienyl
Q 0
hindered
The activation
of LMII(CO)~THE
complexes
(7.24;
with
rotation
barrier
complex AGzz8
= ll.4
analogues has been
(L =v-cyclopentaPhMeCN2
gave
R = H and Me).
the The
R
Mn (CO)2L
expected spectra
carbene were
complexes
obtained
(7-C5Hs)Mn(CO)2L,[L CSHIONH,
were
electron
not isolated 136.
for a series
of complexes
= CS, CO, P(OPh)3, The results
C8H14].
increasing
7.23
7.22
7.21
density
P(OMe)3,
suggested
l3c NXR of the-type PPh3,
metal
CS<~O
was a betterfl-acceptor
of the
PBu3,
that the order
at the transition
of
wasand
than C0137.
(7 -cyclopentadienyl)manganese
. r
was AG&_
complex
7.22 and 7.23)
and 7-methylcyclopentadienyl) imine
-: .
spectra
of the cymantrene
L = cs, cs2;
The reaction
acetophenone
of these
in the manganese
The formation
R = H, Me;
(7.21;
of-21-2&3~,
comp&xes:
underwent
and in the chromium
kcal/mole 134.
gav-e .t
(1-cgH5)C'(Co)(~0)C~~="H2. were
the metal-ol'efin bond axis.
for the ligand
= 8.4
and
The temperature
analysed.
around
R = ii,-acyl) in yields
(?..?a;
The %i NMfi spectra
vinylferrocene$
complex
--
cz-25~;
L _.e
co>
.#i$t;
in
_*rj&~y~ph~spg.,le
ultravio&et:light gave-the complex (7.25;
t&z&
of
pp&zJ=ce
L =.PPh,],
_A
similar replacement reaction was carried out with diphenylacetylene.- Treatment of the complex (7.25; L = PPh3) with = hydrochloric acid gave (7-C5H5)Ni(PPh3)C1 and (7'C5H5)&in(CO)2PPh3 in good yields 138 .
The crystal and molecular structure
7.26
7.25
7.24
-cyclopentadienyl)bis(triphenylphosphine)of carbonyl();) manganese benzate
(~-C51i5)itiCO(PPh3)2.C6H6,has been obtained
from three dimensional X-ray data.
The compound has space
group 21 with unit cell dimensi-ons a = Ye83, C = 11.36 8; o(= 69.44O,p=
66.48,$=
67.57';
b-= 14.79, Z = 2.
The
P-&I-P bond angle was 104' and this large bond angle was considered to be a consequence of electrostatic repulsion between the two phosphorus atoms 139 . exchange in
The rate of proton
(tjI-C5H,-)>In(CO)(Ph2PCH2CH2PPh2) decreased in
acetic acid-trifluoroacetic acid mixtures as the acidity increased. stopped14'.
Mhen sulphuric acid was added the reaction almost The rate of-hydrogen-deuterium exchange in the
same molecule passed through a maximum as the acidity was occurred when the concentrations of the protonated and~nonprotonated forms were about equal 141 .
-increased.
Themaximum
The.cymantrene analogues (7.26;
H = CN, NCO, NCS, N3) under-
went addition reactions at the R group-wilth aIcohoIs,-amines le _ =+: _~~~>~~~ se-_Tertiary_add secondary carbinols of cyclopentadienylmanganese carbonyls (7.27) when treated with trifluoroacetic .acid give stable carbenium ions (7.28).
The carbenium ions
were identified by infrared spectroscopy and when one of the carbonyl groups was substituted by a phosphine ligand the stability of the carbeniua ion increased 143. o
The addition
OH
Q
o Q+R1
R2 CF3CO2Ii \
0
iin (co),so2
7.29
7.27
Ll, L2 = CO, PR
‘7.29
3
of excess trifluoroacetic acid to solutions of ( -cyclopenta7 dienyl)phosphinemanganese complexes (7-CTHS)i-InCOL2 and (7-C5Et5);VIn(C0)2L,where L = substituted phosphine and diphosphine ligands , gave rise to a &Yn-H proton NMR signal at 6 =.-4 to -6
ppm.
The stereochemistry of the protonated
forms was determined from the 1H-31P coupling patterns 144. The structure and bond lengths in the Tcyclopentadienyl compound (7.29) have been determined by X-ray methods;
Tht;-
manganese-cyclopentadienyl carbon distance was 2.09 a and appreciably shorter than in cymantrene compounds while the manganese-sulphur distance was shorter -than the normal covalent nond length by 0.3 8 145. Th& infrared and Rarnan spectra of (tj)-C4ilLLN)&ti(CO)3 and the infrared spectrum of (7-C4D4N)Mn(C0)3 were recorded_- _ References
p_ 288
238 and the vibrational frequencies were assigned.
The
frequencies of the C,+H$ ligand closely resembled those of the cyclopentadienyl ring in .(7-C5'~~)~~(CO>~...."~he replacement of a CX group by nitrogen had little effect on the,mechanical properties of the ring and the lowering of the local sy,mmetry of the ligand from _gV C to sS did not split the degenerate modes. However, the modes, active only in-the Raman spectrum of the cyclopentadienyl ring, for the pyrrolyl ligand also appeared in the infrared spectrum 146 . Nucleophiles were shown to combine with the cationic complex four different ways; rf7-C6H6)bti(CO)Jt In to the arene;
(a) by addition
when the complex was treated ivith (Et02C)CH-
it gave[~-C6H6CH(COzEt)z]?fn(CO)j;
(b) by attack at the metal
vxLth displacement of a carbonyl liganci; treaEaent
of the
complex with triphenylphosphine gavl[~-C6H6Mri(C0)2PPh~]*; (c) by attack at the metal with liberation of arene;
treatment
of the complex with methyl cyanide gave ~4n(CO)S(MeCI~)~]+; (d) by addition to the carbon atom of a carbonyl group; treatment of the complex with methanol gave (7-C6i56)Xn(CO)2COz;e147. 8. (Acyclic-+diene)Fe(CO)S
and (r?-trinethylenemethane)Fe(CO)5
complexes YlhenN-pyrone was heated with diirone.nnea carbonyl the tricarbonyliron complex (8.1) was obtained.
The ester group
in this complex zas highly reactive and underwent cleavage with methoxide to .@va the ally1 anion (ij.2).
Treatment
of this anion with acetic anhydride gave the ester (8.3)
and
treatr?lent yiith lithium aluminium hydride gave the aldehyde(e.h)14"..
The reaction of I\ieCH=C~CIi=CHCB(Ie)lUH2 (R = ii,Xe)
/c =n’
239
0
,.---‘,
0
0
t
rr
Fe
(co)3
AC
0
OCH3
Fe
S-2
8.3
with pentacarbonyliron gave the tricarbonyliron complex Alternative routes to this complex were also presented14'.
(8.5).
The reaction of Fe2(CO)v with the olefin FcCH=CHCH(OH)Me (Fc = ferrocenyl) in the presence of copper (II) sulphate gave (rj+FcCH=CHCH=Cii2)Fe(CO)3. In a similar manner FcCMe(OH)CH=CE2 gave (7-H2C=CFcCH=CH2>Fe(CO)3.
The dehydration
/7== \ 0
H
Fe
(CO)
3
8.4
6.5
3.6
of E-PC d CH=CXCH(OH)Me with copper (II) sulphate gave
64
E-FC6H4CE=CHCH=CH2 which when treated with Fe#C0)12 the complex (~-~-FC6H~CH=CKCH=CH2)Fe(C0)3150.
forned
Then:-ally1
lactan (8.6) when heated in methanol gave the iron-tricarbonyl complex (8.7)15". Aumann has obtained the vinylcyclopropane complex of iron
(8.8) from the parent hydrocarbon on irradiation-with iron References p_ 288
When the cyclopropane (8.8)
pentacarbonyl.
was heated in
benzene-it gave a mixture of the (ydieneliron compounds (8.9 &ntzaris
and 8.1C)!52.
and Weissberger have investigated
/\ +‘T,
Fe
(co)q
.
Fe
(CO) 3 8.8
8.9
..
8.10
the mechanism by ;V'hichcyclopentanones are formed through coupling
of olefins to carbon monoxide on irradiation with
iron pentacarbonyl.
Photolytically generated iron
tetracarbonyl first formed a (tj -olefin)iron tetracarbonyl complex which was converted to a bis(7-olefinjiron tricarbonyl complex through the intermediate (q-olefinjiron tricarbonyl. Cyclization to a metallocycle followed by migratory insertion of carbon monoxide led to the product 153 . The structures of two diene-iron tricarbonyls (8.11 and 3.12) having substituents in the ~JI-Iand anti positlons were determined by X-ray diffraction. -
as models for the parent
These_ compounds zere used
compound (q-butadienelircn tricarbonyl _ _
_-
. -.
241
and on the basis of their structures, the-structure (8.13) for the-butadiene molecule bonded to Fe(CO)3 (CSsymmetry) was proposed154.
(7-Pentadienyl)iron tricarbonyl cations may
a = b = c = o(=
3.12
8.11
1.404 B 1.415 1.08 119.8'
-p = 117" II = llYO s= 1180
have the structures (8.14, 8.15 or 8.161, the diene (8.14) and trimethylenemethane (8.15) structures are consistent with the K&N rule with an U-electron
configuration at iron.
However, the ally1 structure (8.16) with a 16-electron configuration at iron is consistent with the Dewar-ChattDuncanson theory of bonding in transition metal'7Gcomplexes. Structure (8.16) permits free rotation &bout the C,-C3 bond while this is not permitted by structures (8.14 and 8.15). Evidence for free rotation has been obtained by Bonazza and Lillya on treatment of the (7-butadiene)iron complex (3.17) The low-temperature with FSO !A in sulphur dioxide. 3 spectrum of the cation formed from the complex (8.17) -ctas not wholly consistent with a (t7-aliyljiron cation 155 .
Fe+ NOI
8.14 References
p_ 288
a.15
8.16
Pe (CO)
a-17
3
.
_
. Kruczynski.and Takats have investigated the fluxional behaviour
of-several (q-dienejiron tricarbonyl compounds-b-y variable .temperature '% RXR spectroscopy. A lox-temperature limiting spectrum was obtained in each case with a 2 : 1 ratio of basal ; apical carbonyl groups.
A mechanism (8.18+8.19=+
8.20) was suggested~for the basal-apical exchange157. .. 1
, CO1
-
7
CO2
I
1
2*/FeY
co3
,,,~
I
e
+
+3 co-’
3.19
8 .I_8
iron complexes. (8.21;
The
,/w\ 0:.
A1
8.20
R = H and Me) were characterized
by protolytic reactions, mass spectrometry and 'H and 31P Mk? spectroscopic studies 1%. R
3.21
Brookhart and Harris have reinterpreted earlier results on the proto&tion.of a general=toGchange
polyolefinic metal complexes 'interms of in metal ligand bonding.
This has
been exe:aplifi.edfor (7-butadiene)iron tricarbony2 (8,221
_. _
,
which gives the-3-allyl G-iron-cation
(8;23) that undergoeses
intramolecular proton scrambling by equrlibration with-a-~ small proportion of the q-ally1 cation (8.24)1=.
nI
--'
+
Fe
'Fe
(CO13
(co)3
8.22
Iron
5.23
8.24
tetracarbonyl and iron tricarbonyl complexes (8.25) of a$-unsaturated
carbonyl conpounds have been treated with
acetylium tetrafluoroborate to give yellow, crystalline air-labile salts which may be formulated as either ally1 (8.26) or enone (8.27) complexes.
These salts are decomposed
easily by nucleophiles such as methanol and water to give the original enone complexes (8.2~)~~'.
8.25
Whitesides and Slaven
::.26
have investigated complex formation between the a-
8.27
and
trans-isomers of Feist*s ester (8.28) and diironnonacarbonyl. -. The first formed products are aand trans-(7-olefin)iron tetracarbonyl compounds (8.29) yfhich then undergo ring opening and a series of stereospecific reactions to give_eventually References p_ 288
.- anti- and syn;&dieneIiron 8.31)
respectively.
*isomer (8.29)
tricarbonvL corn&.e~
(,S,~Qand
.The photochemical reactions of the cis
parallel the thermal reactions whLLe the trans gave a q-ally1 complex 161 .
isomer (8.29)
.
_
The attack of several open-chain pentadienyltricarbonyliron cations (8.32)
on 1,3_dimethoxybenzene has been studied
kinetically.
The trans-pentadienyltricarbonyliron Me0 C
i-ieO,C Fe2(CO)
_9
cation
2\
L
i b
Ple02C
-+
Ie02C
8.28
Gl,
8.29
Fe
m3 8.31
ite02C
1~ -b
\
;-ie02 C \
(E,, 3.30
(8.33) was postulated as the reaction intermediate and only one product (8.34)
was isolated 162 .
iron tetrafluoroborate (8.35)
Pentadienyltricarbonyl-
was treated with a series of
246
either one exomethylene group exchanged:'lithone ring methylene or.that.the hydrogen atoms were reversibly exchanged betvieen 165. The the ring carbon atoms and the exocyclic carbons c~
E2-
H
H2
-*CDT D2c Fe (co)g
2
W C"i2
3 Cj$ '2
IZ2gCIi2 Fe OCo)j
G),
8.45
2.44
3.43
monomer (y-2,4-hexadiene -l-y1 acrylate)tricarbonyliron
(8.46)
was prepared from pentacarbonyliron by the routes shown (Scheme 8.1).
The monomer (8.46)
was honopolynerixed and
copolymerized with acrylonitrile, vinylacetate, styrene and methyl acrylate in the presence of azobisisobutyronitrile as the initiator.
The polymers were characterized by infrared,
gel permeation chromatography, viscosity and differential scanning calorimetry studies.
When the polymers were
166. decomposed_thermally in air iron (111) oxide was formed The crystal and molecular structure of a?-trimethylenemethane complex of iron has been determined by X-ray methods. The complex was formed from diironnonacarbonyl -2(bromomethyl)naphthalene167.
and l-bromo-
The gas-phase infrared and
Raman spectra of trimethylenemethaneiron tricarbonyl were recorded and interpreted 168 . The butatriene derivatives
-
_
247
8.46
Scheme
(8.&a;
Rl = Ph;
8.1
R2 = t-Bu, e41eC6H4, p-MeOC6H4, Ph,
o(-naphthyl; R3 = Ph, t-Bu, z-MeC6H4, &-MeOC6H4; t-Bu, Ph, E-NeC6X4, &4eOC6Hk,
R+ =
o(-naphthyl) gave a series
of complexes with Fe3(CO),16g. R1 \
I<3
C=C&=C
/ ,22 9.
/
8.46a
>4
(q-C,,H,,)?e(CO)
3
9.1
The carboxylic a&d References
p. 288
9.2
9.3
(9.2) has been synthesized conveniently
248
-
by irradiation of the pyrone (g.l),.addition of an excess of iron pentacarbonyl to the photoproduct-and further irradiation. The product (9.2) was obtained in 21% yield after saponification and the intermediate ester (9.3) was also isolated The isomeric tetrahalocycloas a light sensitive oil 170 . Br
Br 9.6
9.4
butanes (9.4;
R1 = R2 = H or He) were treated with Fe2(CO)g
to give the cyclobutadiene complex (9.5;
R1 = R2 = C02ile).
This complex was converted to the optica$ly pure Complexes and R' = (9;s; R1 = Et, R 2 = tie; R1 = C02xe, R2 = COIule C02S, R2 = COMe)171.
Methoxymethyl-3, 4-carbonyldioxycyclo-
F 0
d
9.3
0”: 0
0
9.9
butene was treatetiwith disodium tetracarbonylferrate to give (q-methoXymethylcyclobutadiene)iron tricarbonyl which was converted to the bromornethyl derivative (9.6) acid;
by hydrobromic
The treatment of this derivative (g-6) with potassium
249
(coLj 9.10
9.11
alkoxides gave the complexes (go7;
n = 1,
a.
Successive
photolysis and Ce (IV) oxidation of the complexes (9.7; n = 1, 2
gave 5-methylisochroman (9.8) and 4-methylphthalan
(9.9) respectively172. By the use of reasonable approximations a valence force field has been calculated for tricarbonyl(T-cyclobutadiene)iron using s4x symmetry for the C4H,+ group and + RFe(CO)g moiety.
for the
The results obtained reproduced the observed
vibrational frequencies very closely and were consistent with those known for related systems173. complexes (9.10;
Irradiation of the
R = But or Ph) in hexane afforded the
binucleer derivatives (9.11;
R = But or Ph), these complexes
were converted back to the starting materials by treatment with carbon monoxide. (9.11;
The crystal structure of the compound
R = But) was determined by X-ray diffraction.
The.
two iron atoms were bridged by three carbonyl groups and the cyclobutadiene ring was essentially square planar.
The
Fe-Fe bond was extremely short, 2,177 8, and it was thought that a triple bond existed between the t%ioiron atoms.
This
gave the iron atoms eighteen electron configurations and it also accounted for the diamagnetic behaviour of the complex 174 o The structure of (tj3-cyclobut&diene)iron.tricarbonyf has been studied by microwave spectroscopy and it has been References
p. 288
J ’
confirmed spectra obtained
as
symmetric-top
of-(7-cyclobutadiene)iron for the liquid
and 13C NMEtspectroscopy between:the
phenyl
tricarbonyl
group
‘Tne
tri&.rhonyl
and solid
frequencies assigned176 .
175 _
molecule
phases
IR
and
Raman
have been
and the vibrational
Brune and Horlbekk have used 'H to investigate
substituent
and the
in the complexes
electronic
interactions
(?J-cyclobutadiene)irod
(9.12;
R = H, F,;Cl, Br).
group donates eILectrons,by conjugation The:(t)-G4H3)Fe(CO)3 and accepts electrons molecule177,
through
The 100 i%&
the S.&PAZLskeleton
of i&e
'H M4R spectra of chloro-, bromo-
and methyl-cyclobutadieneiron
tricarbonyl
were recorded
and
analyzed178.
The ca.rbaxy3.i~ acid addition
(9.13)
has
of trichloroacetonitrile
tricarbonyl-and r-k&rw~~&~~
alkaline_ hydrolysis
imtanvadfate.
been prepared by Hoes&z-
to (v-cyclobutadiene)iron of>the
-The acetic
resulting-.tri-
acZd
derL.ative
__
<4,1%>~
was obtained-by displacement of chloride from C?&hXoromethylcyclobu~adienefriron tricas%onyl: uriQ~ cyanide and hydrolysis of the acetonitrile derivative. aGa&. as
cgmYL_3cizK%?8.14)
5.C33
Mt?idS--It
5.56
end WSS
CtSnC~CC&?~
The PK, values for-the two
in Jx?$
wer-e %zeasur&
respeciXvely. t&St:
.
ef&zal
aqueGzzs
Gn the %asis of t&es6 measure-
CrT-cycl~~~tra~~ene)~rU~
k~~CZII%KXS~~
is an erectron releasing group by resonance and a weak electron withdrawing group hy induction 179, q-~c~tyzrgc~o~~tadieRa}iroR
pin‘acol-reduction of
triCEtX%ORy~
~gZk+S
t&3
#-C-ii&
(9.15)
which'was dehydrated to-the diene (9.16) and underwent pinacol rearrangement to the ketone (9.17). -- Reduction of the same acetyl derivative
with
diborane_ gave
(v-ethylcyclobutadiene)-
iron tricarbonyl and acetylation of this product gave a 9 : 11 mixture of the 2- and 3-acetyl derivatives.
Treatment-of
(v-acetylcyclobutadiene)iron tricarbonyl with base led to the isomer-it dypnones ~9.~@0.
OH
Grey has descr5bed the
OH
5+--T 0
0
fe
Fe
(co>3
(COlg
9.16
9.17
9.18
252
.
decomposition of an optically active (7-cyclobutadiene)iron tricarbonyl derivative with ceric ammonium nitrate in the presence of dienophiles to give totally race&-products, These results supp0rted.a mechanism of decomposition where 'free cyclobutadiene was an intermediate 181 . The iron carbonyl cation (9.19) has been formed by hydride abstraction from a benzocyclobutenyl precursor.
The structure
(9.19a) is preferred to the alternative (9.19b) on chemical grounds
and
degradation through
the
it
may
be
of
(7 -cyclobutadiene)iron
sequence
an
intermediate
the
o-dative
tricarbonyl
182 .
(9.20.+_3.24)
@+
in
complexes
Irradiation of the
-g+
F&(C0)2 I .-w\ \ .‘1
Q V.;Vb
9.1?a
n+
n+
7 G
>
la’
01 '7
Fe
Fe
(CWg 9.20
9.22 nc -
7
9.24
1
Fe
(solv)
B-1 3.23
253
benzocyclobutadiene complex (g-2.5)with iron pentacarbonyl gave the diiron complex (g-26) as the major product together with minor amounts of two isomeric diiron complexes (9.27 and 9.28)
and two triiron complexes (9;29 and 9.30).
complexes (9.27 and 9.28)
The
were formed by an unusual ring-
-opening of the cyclobutadiene group and gave the triiron complexes (9.29 and 9.30) respectively by coordination of a third iron tricarbonyl residue 183 _
Fe(CO> 3 \
(CO)3Fe-qT5;3
v7cCo)3
+ q&o)3
+ 3 g.23
Fe w3
9.29
9.30
Fe w3
(3-Cyclobutadiene)iron tricarbonyl was stirred with nitrosoniurs hexafluorophosphate in acetonitrile to give the
PF
9.33
6
air-st~b~e__cryst&ine addition-of
trialkyl
butadiene. cation When
complex or triaryl
(9.31)
the hydrocarbon
complex
by heating
Complexes.
under
complex
with diiron
then the complex _
to the 7-cyclo-
diiron
nonacarbonyl
of carbon
monoxide
in to
An iron carbonyl
control
nonacarbonyl
cp. \- +
gave
from the reaction
nonacarbonyl.
of homosemibullvalene
10.5 and 10.6)~~~.
~- 10.3
(9.32).
(i) Formation
(10,1)186.
(10.2) was obtained
under kinetic
I
complex
10.2
[4.1.0]heptane
diiron
with
an atmosphere
10.1
reaction
phenyl
in acetone
dimer was cleaved
the pentalene
derivative
to the ?-cyclol
(9.33)185.
methylcyclohexane give
phosphines
(H) were
10. _(Cvclic-n-diene)Fe(CO)z
Pentalene
Eucleophilic
gave the .q-cyclobutenyl
groups
(9.32) was converted butadiene
(9.31)&*4_
The reaction with
Fe(CO)5
The light-induced
(10.3) with
the iron
benzo[&]
hy
pentacarbonyliron
carbonyl
of iron
of bicycle
compounds
pentackbonyl
thiophen-l,l-dioxide
I CD
(10.4, or gave
\ -Fe(COj4 .
10.4
.
10.6
10.5
the two co:aplexes (10.7 2nd X.8).
- The structure of complex
(10.8) was confirned by X-ray crystallography188.
10.8
10.7 iron carbonyl complex (10,9;
The diene
10.9
-
R' = alkyl, R2 = H) was formed by
treatment of the appropriate silacyclopcntadiene aith diiron nonaThe same complex (10.9; R1 = alkyl, R2 = ii) czrbonyl 189. y{as
ureParod-independently by a second group using the same *
reactant&.
The corresponding tetraphenyl complex (lO.g;* R" = _ .
alkyl, R2 = Ph) was also prepared from the tetraphenylsilacyclopentadiene 2nd iron pentacarbonyl. R1 =
Xe,
The complex (10.9;
R2 = Ph) was obtained from_l,l-dimethyl-2, 5-diphenyl-
silacyclopentadiene
by treatment with bromine to form 2 .
mixture of the ,?,3- and Z,5-dibromo adducts which were then .= heated with diiron nonacarbonyllgo. Photolysis of pentacarbonylfron and the 2-vinyloxiranes (10.10;
33 = H,
ReferenceSp.288
Me;
X i “H2,
_
CH2CH2> gave the lactones (10.11).
iTlien the
la&one
(lO.11;
H = k, X = CH2CH2) was heated- in
benzene the complex (10.12) was formed w_
Treatment of the
cyclohexene (10.13), prepared from l(diethylamino)butadiene and Cki2=CkJR, with Fe3(CO)p2 gave the Irontricarbonyl complex (10.14; R = CHO,
COble)192.
The cyclohexa-2, 4-dLene c~p~ex
ILo,
10-14
(10,Is)
10.15
was prepared by heating the correspond%ng cyclohexa-2,5-diene with iron pentacarbonyl.
The rearrangement may occur by a
l,s-hydride stift frozna methyl. grozp to the exomewiglene grou_n in &&ch
the iron carbonyl group participates 193 -
The
stereochemistry of the interaction between diiroa nonacarbonyl and cisoid or transoid divinylcyclopropyl ligands has been examSned by ~zsing the spir0norcaradiene (10.16) as the ligand since
this
ligand contains both cisoid and transoid systems
in the sazzemolecu1e*
S==Id conditions (room temperature,
257
10.18
10.16
Details were given for the preparation of tricarbonyl(v-2,4-cycfohexadienone)iron and tricarbonyl(t?-2-methoxy-1,3-cyclotexadienylium)iron hexafluorophosphate from anisole l%,l%_ Their conversion to tricarbonyl(l-ethoxycarbonylmethyl-l-hydroxy-2,4-cyclohexadienejiron
(10.19) and tricarbonyl
~?-(2-hydroxy-4,4-dimethyl-6-oxo-l-cyc~ohexen-l-yl)-2-methoxy-l,+cyclohexadiene]iron
X0
cii2c025t
0 \’
I
I
(10-20) respectively was described1g7S1g8.
258
Dodman and Tatlow have described the preparation of some (7-polyfluoro-1,3-cycloheptadiene)iron (10.22;
tricarbonyl complexes
X = H, F) from tr~Grondodecazarbony1 and the ligand
in sealed tubes at 130°.
Pyrolysis of the complexes at 440° C
under nitrogen gave polyfluorobenzenes, presumably by loss of iron tricarbonyl and fluorine to form polyfluorocycloheptatrienes Yfang and Paul have prepared an land then ring contraction 200 . iron tricarbonyl complex of barbaralone in which.the hydrocarbon
may be bound as a uhomobutadiene" ligand (10.23)-
This
proposal is-supported by X-ray structure analysis and molecular spectra201-
Details have been given for the
synthesis of bis(v-1,3,5,7-cyclooctatetraene)iron tris(2,&pentanedionato)iron,
(0) from
1,3,5,7-cyclooctatetraene and
triethylaluminium202, The cis4 -cyclononatetraene conrjlex (10.24) has been _ . prepared from a-bicyclo[6.1.0]
nonatriene either thermally
v:ith diiron nonacarbonyl or photochemically vrith iron pentacarbonyl.
Three other (7-CgHLo)iron carbonyl complexes
were isolated and characterized from the same reactfons. W-iile the parent hydrocarbon ligand underwent rapid electrocyclic ring closure to dihydroindene at 23O (t+
= 50 JKL~,
259
dF*=
23 kcal mol'l); the complex is stable at room temperature
for several days hut underwent first-order isomerixation to .
the dihydroindene complex (10.25) at 101' (k = 2.4 x 10m4 set -l, BFf= 28.4
kcal mol -5 .
Protonation of the tetraene
compound (10.24) occurred at C6 in FSO H at -120' to give the 3
dienyl cation (10.26)203.
/\ \ 0
The reaction of 1,7-cyclododecadiyne
H2
+
1
H2
'/ I
Fe
G,,
(co)3
10.24
10.25
10.26
(10.27) with Fe(C0)3 unexpectedly gave the ferroie (10.28) rather than the ferrole (10.29)204.
It was suggested that-
the formation of (10.28) proceeded through the (r;)-cyclobutadiene)iron tricarbonyl complex (10.30) from (10.27) and Fe(C0)5, and further reaction of the complex (10.30) with Fe(C0)5 to give the ferrole (10.28).
This suggestion was supported'by
the combination of the iron tricarbonyl derivative (10.31) with excess Fe3(CO>12 to afford a mixture of the sym- and unsym-benzoferroles (10.32) and (10.33) respectively205,
10.27 References p. 288
10.28
-260
Irradiation
iron cations
of (v-dienyl)tricarbonyl
n = l-3, R = ii, ONe) in the presence l,+diene
gave
R1 = If, OXe; of these reagents
10.33
10;32
3_0*31
the cations
(10.35;
(10.34;
of the appropriate m = 0, 2, 3;
n = 1-3;
Rz = H, Xe) in good yields.
The reactivity
cations
towards nucleophilic and electrophilic 206 In an investigation of the photo. was examined
Fe
(SO)
3 10.35
10.34 -reactions 3-hexyne chloride
of cyclopropylacetylenes was irradiated
with
with iron
iron pentacarbonyl
carbonyl, in rnethylene
to form the benzoquinone adduct (10.36) in addition 207 . The irradiation of Fe(CO)5 to the free benzoquinone
261
Et
Et
0
i30
_I_ I
Et
(Ei,
I
zt
Fe 3
(CO)
10.36
3
l-O.38
with cycloocta-1,5-diene and cycloocta-1,3-diene gave the corresponding (y-diene)irontricarbonyi complexes (10.37 and 10,38).
On reaction
-ion abstraction
of complex
occurred
to
complex ~'I-C&1)Fe(CO)3]+ The direct
reaction
(10.38)
give
the
with Ph3CBF4 hydride-
cyclooctadienylium
208.
of pentaborane
(9) with
the reaction of tetraborane (10) with Fe2(C0)9
ferraborane B4H8Fe(C0)3 (10.39).
Fe(CO)5
or
gave the stable
Spectroscopic evidence showed
that the i?e(CO)g group had replaced
the .apical BH group in
B5k19and that tke compound had structural and bonding affinities y/ith (7-C4H4)Fe(CO)3
and Fe5(C0)15C
2og.
0
0
a aD 0
(ii) S;ectrosco:>ic The structure
References
p_ 288
II Fe 0
c 3
and Physico-chenical
of the tricarbonyliron
10.39
%udies coiplex
(10-40)
262
The Fe(C0)
was determined from X-ray data.
3.
moiety was t
bound to-the diene portion of the cyclohexadiene ring and this six-membered ring was e-fused
to a four-membered ring, ?zhich
in turn was cis-fused to a second four *membered ring. . Both 210. The molecular four membered rings were essentially planar structure of the (q-diene)iron compcund (10.41) has been The ligand determined by single-crystal X-ray analysis. The crystal and molecular adopts the boat conformation 211 _ ‘.r(i H-3
1e f
OTC)= 0
7 G,, .
Fe
WO13 10.40
10.41
.
10.42
structure of 3,35'-bi8(7-bicyclo[4.2.0]octa-2,4-diene-tricarbonyl-ironj, analysis.
C(~-CgHg)Fe(C0)~2
was determined by X-ray
Phe structure consi8ted of two bicyclo[4.2.0]octa-
2,4-diene-tricarbonyliron moieties related by an inversion centre212.
Struchkov iias reported bond lengths based on
Z-ray neasurements for the iron complex(10.42)213. has
determined
tke
bond
length8
and
Struchkov
interatomic‘distances in
the cyclopentadiene complex (10.43) by K-ray method8213. The structure of tto iron complex (10.441,
containin&, two r different valence-tautoueric forms of thev-C8Hlo~ligand,
has been determined by x-ray crystallography.
90nd length
alternation in the parts of the ligand8 bonded to the iron atom was not observed and these parts of the ligands were planar214.-
The crystal and molecular structure of a tri-
263. carbonyliron derivative of barbarlone (10.45) has been determined by X-ray cry.stallographSi. The compound crystallized
/-4 0
7e(CO)3
L -. --2s
10.43
10.44
10.45
from pentane at -5' in the triclinic system with unit cell dimensions a = 7.48, b = 11.91, c = 6.61 8,oC= 94.55', /3= 110.17', y= 92.38', 2 = 2 space group l??carbonyl groups were mutually cis.
The three
The ally1 group was
trans to two of the:aand the Fe-C sigma bond was trans to the third carbonyl group 215 . The 57 Fe Aoessbauer spectra obtained on glassy n-butylbenzene matrices of the tricarbonylferroleiron tricarbonyl derivatives (10.46, 10.47 and 10.48) were analysed. The two nonequivaLent ircn atoms were resolved and the doublet with a quadrupole splitting in the range ~22-1.26
mm/set
was assigned to the iron atom of the iron tricarbonyl group bonded to all-four carbon atoms of the ferrole ring,
The
doublet at-a less positive isomer shift with a quadrupole splitting in the range 6.9$/1.02 mm/set was assigned to the iron aton-in the ferrole ring 216 _ The electron-impact induced fragmentation of thirty derivatives of the styrene complex (10.49) has been studied References p. 288
_ m-m
g--L
mym
f
.(Cqn
$
-A
(S5
Fe (CO) 3
\
2)n
Fe(Co)3 \\ Fe(CO)3
Fe
("X2)m
(co)3
*.
-10.46 R = Xe, Et, Ph
by -mass spectrometry.
10.47 fi = 4, 5, 6 Zl1= 4, 5, 6
10.48
In each case the complex underwent
stepwise loss of carbon monoxide groups followed by loss of iron atoms as in the following scheme (Scheme 11.1)
~~-vinylstyrene)l?e2(C0)6]'_
kv-vinylstyrene)Fez]' .
[Q-vinylstyrene]+
C--
t(T-vinylstyrene)]Fe+ 3
Fragmentation of the organic ligand was sensitive to the nature and position of the substituent, at least four modes of breakdown were observed 217 . Infrared and Raman spectra of (~-N-methylmaleimide)iron tetrac-arbonyl (solid, solution) and of N-methylmaleimide (solid, solution , gas) were recorded.
An assignment of the
normal modes of both molecules was made and compared with the data for (q-maleic anhydride)iron tetracarbonyl.
The C=C
stretching vibration in the complex occurred at 1370 cm" co.mparedaith 1585 cm-1 in the free ligand218.
as
Andrews and
Davidson-have also investigated the vibrational spectrum of (q-maleic anhydride)iron tetracarbonyl.
On the basis of
265
solid-phase infrared and Raman spectra,' together
with
some
solution data for the infrared, a complete-vibrational assignment was made for the modes of maleic anhydride in the complex. Shifts in 3(C=C) and 6(Cii) were consistent with a strong interaction with the metal, but relatively little coupling between the modes21g.
These.results agreed in all essential details with those presented by Lokshin and co-workers 218 .
10. (iii) General Chemistrs Treatment of the (7-cyclohexadienyl)iron tricarbonyl cation with sodium alkoxide (NaOR) gave the iron containing cyclohexadiene ethers (10.50; in good yield,
R = Pa, @GeOC6H,+, 3,_5-;'re2C6H3)
Treatment of the same cation with (v-5-hydroxy-
-1,3-cyclohexaciienyl)iron tricarbonyl gave the ether (10.5~1)~~~.
Fe
Fe
GO)3
(CO13 10.51
Irradiation of (v-g-quinodimethane)tricarbonyliron in the presence of pentacarbonyliron'gave the t'hree isomeric complexes
.-,
--
_
_:
(10.52,
X.&and
10.54)zz1.
has been-shown aromatics. benzene
The dienyl
to act as an electrophile
Thus
l,+dimethoxybenzene
gave the diene-substituted
following
reaction
(Scheme
/--.+ (.I_: ‘0.
cation towards
benzenoid
and 1,5,5-trimethoxy-
Rroducts
10.2).
(10.55)
Rate
(10.56)
constants
in the for the
1
BF4-
+’
_*s
I I
10.55
Fe
(co>3 Scheme
reactions
were measured
for the reaction
10.2
and compared
of the cation
to give the order
kth
(10.55)
the rate
with some
heterocycles
nyrrole?indole>
of reactivity:
constants
furan)
1 ,3,5-trFmethoxybenzene>l,j-dimethoxybenzene)thiophen. Preliminary
experiments
;'rasalso an active
indicated
electrophile
that
[(v-C71$.)Cr(CO)3]+
towards
heterocycles
such as
-indole222. The pentadienyl the diene
complexes
cation (10.57;
vfith tri~A~enylmethy1 cation
(10.<9;
these
cations
the diene
complex
(10.60)
Ii = Xe) .
enamines,
li'thiums have been studied.
formed
from
by treatment
The methylpentadienyl
formed under
(10.57;
(10.59) with
R = a) was
R = I-I and 10.53)
fluoroborate.
R = fie) was
fro.5 the diene.complex
(10.59;
the same conditions The reactions
alkoxides
The cation
on treatment
..
of
and alkyl-
(10.59;
R = II> gave
with alkoxide
ion andd
Q \I / I Fe
OS3
with the enamine (10.61) it gave the complex (10.62) after hydrolysis223.
Experimental evidence has been offered to
support the hypothesis that (v-cyclobutenejmetal complexes can undergo a facile, disrotatory, concerted rLng openin& of the complexes, four-membered ring to give ( -butadiene)metal 7 The iron-olefin complex (10.63) has been heated in hexane to form the iron-diene complex (10.65) presulqably through the intermediate (10.64). to solvent
The rate of.conversion is insensitive
polarity.and the reaction is inhibited by carbon
monoxide and added olefins 224.
~.
--:. The reaction of (7-bicyclo[3.1.O~bctadienyl)Fe(CO)3~ --CXOi66) vfifh pyridine gave the cyclooctatriene complex (10.67) -_ .. which-was . transformed into the corresponding cyclooctatetraene .. complex (10.68).
The addition of iodide ion to the complex
(10.66) caused the cyclopropane ring to open to give (3,&,5-~-octatrienyl)Fe(CO)-J225.
The fluxional cation
+
I
Fe (CC) 3
Fe (co)j
lo.66
i-
10.67
inJ+
10.63 (10.69) was prepared by acid treatment (HBF,+-Ac20) of the alcohol (10.70) or its isomer (10.71). ,
Treatment of the
cation (10.65) --ith triethylamine gave the dimer (10.73) via the unstable (7-heptafulvene)iron tricarbonyl complex (10.72). The structure of the dimer (10.73) was confirmed by an X-ray investigation 226 .
+ 1
i69
w 1’
\I
1
\.I/-
I
I
Fe
Fe
(co)3
10.72
GOI
IO.73 of solutions of (r)-cycloheptatriene)iron
Irradiation
tricarbonyl and acetylene dicarboxylic ester in tetrahydrofuran gave the complex (10.74).
6fi]addition had taken place and
demonstrated that [k+ X-ray data indicated to the triene bonded.
that the acetylene
on the same
This
The isolation of this compound
suggested
moiety
had added
face to which the iron atom that at some
xws
point in the reaction
the acetylene was bonded to the iron atom.
Irradiation of the
complex (10.75) with acetylene carboxylic ester gave the complex (10.761~2~.
The reduction-of tricarbonyl(l-_5-7-
-cycloheptadienylium)iron with sodium tetrahydroborate resulted
$-Jy2- PO) 2-e
(co)3
CO
lo,742
.2e
Fe
GOI
10.75
in nucleophilic attack at both the l- and 2-positions to generate
a mi.x*Jre of tricarbonyl(7 -cyclohepta-1,3-diene)iron
(10.77)and tricarbonyl(3-5-7,l-Ckyclo-heptenyl)iron Tricarbonyl(l-T-7-cyclohexadienylium)iron
(10.78).
and its dicarbonyl-
(triphenylphosphine) analogue both gave the corresponding References p. 288
.-
10.73
10.77
10.79
cyclohexa-1,3-diene product (10.79; L = CO and P?h3> when 228 . treated withsodi&tetrahydroborate The mechanism of the thermal isomerization
_
of the octa-
tiene complex (10.80) to the more stable complex (10.82) has been investigated.
b-V Tne reaction foll.owed first-order
kinetics with a free energy of activation of 31.3 kcal mol'I. Both kinetic and analytical evidence indicated that the cycloocta&iene
complex (10.81) was the intermediate in
the rearrangement22g.
Thermolysis of (7-a-bicyclo&,l.O]
p-0
I
Ye
Fe
(CO> 3
(co)3 10.81
10.s2
nonatrieneldiiron hexacarbonyl (10.83) involved rearrangement of the organic ligand to give four iron (10.84, 10.85, 10.86 and 10.87)230.
carbonyl complexes
i'ihenthe cyclooctatetraene
R3 = i!, 3' CPh3) tiere heated-in a sealed tube in octane they rearranged complexes (10.d8;
CPh R1 = Ii,SiNe3, R2 = -'-,
to give the isomeric bicycle. [4.2-O] 2,4,7-octatriene compounds iXo.sg;- 4
= SiMe _.3, CPh3, X2 i H,Si>Ie3)~
.
The crystal and
.
271
m ‘iFXFe c-
-I-
:
I
\
/
\
&
1
(CO13
(COj3
molecular structure of the complex (lo-S91
•!-
/b I I J,
10.85
I/
A
Fe-Fe
10.86
(c0),(c0~, was determined
by X-ray analysis231.
via
The synthesis of bicycle [6,2;0]decapentaene derivatives 232 . the tricarbonyliron complexes has been reported
Kinetic studies were carried out on the reactions of tricarbonyl(7-cycloocta-1,3-diene~.-,tricarbonyl(7-cyclohexa-l,3-diene)-, and tricarbonyl(7-cyclohepta-1,3,5-triene)-iron couqlexes with triphenylphosphine.
In the presence of excess
triPhenylphosphine tricarbonyl(7-cycloocta-1,3-diene_)iron underwent a second-order process to form trans-[Fe(CO)3(PPh3)2].
In contrast, tricarbonyl(i')-cyclohepta-l,+diene)iron and ~_ tricarEonyl(q-cyclohexa-1,3-dienejiron e-
.<~~
did not combine with
The Gtter complex underwent a PPh, under these conditions. /CO-dissociative reaction at high terfiperatureswith retention of the olefin.
-cyclohepta-1,3,5-triene)iron Tricarbonyl(rjr
was similarly-unreactive but it underwent reaction with
Pph
3
at l.Y+°Cvia first and second order processes 233.
11. (?-C5H,)Fe(r)-C~E6)f " , Ferrocene, in the presence of aluminium chloride and aluminium, attacked a number of polyaromatic molecules to give derivatives of the (q-benzene)(q-cyclopentadienyl)iron cation. Biphenyl, diphenylmethane, fluorene, g,lO-dihydroanthracene, g-terphenyl, anthracene, phenantzhrene, pyrene, chrysene and other aromatics each bonded two (y-cyclopentadienyljiron groups to give dications which were isolated as the yellow hexa-fluorophosphate salts.
The structures of the salts were
determined by 13 C Ni-II? spectroscopy and those of 9,10-dihydroanthracene
for
the complexes
(11.11, terphenyl (11.2) and
phenanthrene (11.3) are typical 234 _
Electron-rich aromatic
compounds behave as donors towards-bis(v-hexamethylbenzenejiron (II) hexafluorophosphate and give 1 : 1 molecular complexes,
273 Benzene,.antbracene, anilines, hydroquinone, pyridine, furan and ferrocene have been used as donors,
In the last case
the-complex (11.4) appears to have four stacked rings 235.
The treatment of bis(rjl-nesitylene)iron(II) hexafluorophosphate (11.5) v.ith a series of nucleophiles (N) gave the mono adducts (11.6; N = CIT, CH2N02, CmleN02, CH2C02Bu t ). The reaction of (11.5) aith several oxygen and nitrogen nucleophiles (e.g. IJeOLi and H2HLi) gave the same product (11.7) which was thought to be formed by the initial attack of a base on anti-proton of (11.5) followed by carbanion addition to another ion (11.5) and finally fragnentation 236 .
(q-i3enzene) t
d’ P 0
_
d P
,.-4
‘
0
le
0
11.5
‘._H
Fe
D 0
11.6
Fe
PF,’
0
11.7
(7-cyclo?entadienyl)iron exhibited a reversible anodic References p. 288
0
polarographic wave at E3 = 1.23 V and an irreversible cathodic wave at E, =--2.19 V, both of these waves involved a single electron2% _ Bennett and Smith have prepared (7-arenejdi-p-chloro-ruthenium complexes (11.8) by dehycirogenation of the appropriate cyclohexadiene with-ruthenium (III) chloride in ethanol., .
.
These
complexes are cleaved Xith grcup V ligands to forn mononuclear complexes (11.9;
L = PH3, AsR3, pyridine) that are formally
analogous to benchrotrene.
The arene groups in the complexes
(11.9) say be exchanged on heating or irradiation in an aromatic solventz3'.
n
Giethylferrocene carboxylate
xas
treated with lo3RuCl 3 to give methylruthenocene carboxylate -103&39_ The IH spectra of ferrocene, ruthenocene and osnocene were obtained .
from monocrystal films and the Laser-Raman spectra were also obtained fro-msolid
samples.
was recorded for a solid film.
The IR spectrum of niclrelocene Fundamental symmetry forbidden
modes were observed for these solid state spectra and the fundamental vibrational modes were assignedz4'.
The
temperature dependence of the ghotoluminescence.of ruthenocene has been investigated by analysis of the luminescence decay
times in the temperature
range
4,2-77B-R,.
The energy
levels
of the lowest
excited states together with their decay character-. vfere obtained and were used to describe-the splitting
istics
of
a 3El(ddj
term into A
spin-orbital
coupling.
luminescence
spectrum
+ A 1 + El t E2 components
2
A J?ranck-Condon analysis
benzene
on polystyrene
beads
have different
that separation
occurs
of the cation with iodine,
(12.1),
the iodine
ligand
are reduced
rings
by 16'.
by 0.01 8.
have been
expected
oxidation
state
has been
coefficients
by X-ray
This shortening
of ruthenium
indicating than
structure
of ruthenocene
crystallography.
and tilted
back
from
bond distances
is less than would
of the increase from Ru
The three
rather
and molecular
The metal-carbon
in view
examined..
by the oxidation
are eclipsed
and
27; divinyl-
interaction
The crystal
has been determined
The cyclopentadiengl
with
distribution
formed
ruthenocene
crosslinked
by solute-gel
sieving 242 .
by molecular
13.
of ferrocene,
and s.:ollen in cyclohexane
metallocenes
of the
at 4.2O K was made 241 _.
The gel c!rromatography osmocene
by
in the formal
(II) to Ru(IV)243.
w-c,~H4)coo7-c~H) 3urther
been reported.
References
p_ 288
routes
to the q-cyclobutadiene
q-Cyclopentadienylcobalt
complex
dicarbonyl
(13.1) was
have
treated with bis(trimethylsilyl)acetylene
to give a binuclear
intermediate which formed the product (13.2) after reaction with a second molecule of-the acetylene.
Heating cobaltocene
with the-same acetylene also gave the complex (13.1). yields were obtained in
Q 0
i-ie3Si
Xe3Si
case 244 .
each
Low
The reaction between
Q 0
itosiHe3 0
xx
SiBe3
Ph
Co SiXe3
-YX Rl
0 R2 13.2
23.2
J-3.3
(7-CyClopentadienyl)dicarbonylcobalt and phenylethynyltrimethylsilane produced a number of organometallic products (13.2, R1 = Ph, Sine=., R2 = Ph, SiNe3; 13.3, RI, R3'= Ph, R2, R4 = SiNe R2 , Ii4 = Ph, Rl, R3 = SiHe R2, R3 = Ph, Rl, R4 = 3; 3' SiRe3) but no cyclotrinerization products were isolated. The structure of one of these products (13.2, Rl = Si& 3, R2 = Ph was determined by X-ray analysis.
The cyclopentadienyl rinb
was planar and had nornal Co-C and C-C distances.
The
cyclobutadicne ring was planar and the four C-C bond distances were equal.
The internal angles of the ring :fere not 90'
but the tivoangles at the carbon atoms bonded to phenyl rings were 88.1-O ar?d 88.4' iJl:ilethose bonded to silicon had values of 91.6~ :lnd g1,8°24so l,+Dilithiotetraphenylbutadiene
combined with
(7-C5H5)Co(PPh3>12 to give (q-cyclopentadienyl)(7-tetraphenylcyclobutadiene)cobalt246.
X-ray diffraction data has been
used to determine the crystal and molecular strilctures of
(7-cyanocyclopentadienyl)(?-tetraphenylcyclobutadiene)cobalt, (7-iodocyclopentadienyl)(17-tetra~henylcyclobutadiene)cobalt and (7-1,2-diiodocyclopentadienyl)(7-tetraphenylcyclobutadiene)cobalt.
In these compounds the cobalt atom was sandwiched
between parallel Ij)-cyclopentadienyland ?-tetraphenylcyclobutadiene rings which were planar.
The perpendicular distances
from cobalt to the plane defined by the five- and four-membered rings were 1.68 and 1.70 8 respectively.
The phenyl groups
were slightly bent away from cobalt with respect to the plane of the cyclobutadiene and they were twisted about their respective axes by an average of 35O in a propeller configuration 247. The borabenzene sandwich complex (13.4) when treated with diphenylacetylene in a sealed tube for seven days at 150' gave (~-l-methylborinato)(3_tetraphenylcyclobutadiene)cobalt (13.5)248.
King and 'co-workers have extended their investigations
G
!3-Ke
0
6 0
l
13.4
13.6
1305
of macrocyclic alkadiyne-transition metal complexes to include the complexes (y-C5H5>Rh(alkadiyne) which were formed by heating (?7-C5H5)Rh(CO)2 with alkediynes in cgclooctane. Five alkadiynes were used and
in each case intramolecular
transannular cyclization was observed to give the tricyclic I7-cyclobutadiene compounds (13.6; m = 5, n = 5 and 6)24g. References
p_ 288
m = 4,
n = 4, 5 and 6,
278
-Harder, Dubler and ?/erner have reported the preparation. and characterization of the trinuclear cobaltocene analogue The crystal and molecular structure of
(14.r>25°.
F ) was determined by X-ray diffraction. "7-c535'co~-c5'y41 B9C2-11
The species crystallj_zed in the centrosymnetri~ monoclinic viittr a = 10.02, b = 10.Y9, c : 14.55
space group
E2r/c
p=
v = 1585.2
98.57O,
if and Z = 4.
8,
The molecule was
z,vj_tterionicand was formed from a cobalticinlum cation and a p9CZH12]bond Wth
anion :lhich were linked via a carbon-carbon
concomitant loss of a terminal hydrogen atom from
each s;;ecies to give the molecule (~-C5!4)C~(?_G5~f~.BgC2~ll)2~1. Cobaltocene isolated in neon, argon 2nd krypton matrj.ces :;as studied by ES? at 4.~~ i-.:. Zarlier results were also considered and it was concluded that the orthorhonbic splitting Paraneter
S (measuring
the deviation from exact five-fold
symi:etry) increesed in the host series ruthenocenenickelocene ( neon < argon < krypton from lob cmi1 , to approximatei$- 3550 cm-1 . iZo
'The 13C iGE? spectra of (7-indenyl)chromium
tricarbonyl, bis(q-indeuyl)iron,
bis(q-inde_nyl)cobaIt
279
hexafluorophosphate and analysed
with
and bis(t?-indenyl)nickel reference
In the case of the nickel shown
to be a trihapto
-deuteriun
exchange
complex,
The rate
in cobaltocene
reaction
ligand
in basic
state
group
Was
of hydrogen-
I
media was slower It was concluded
tetrafluoroborate.
the oxidation
recorded
bonding,
the 7-inaenyl
ligand 253 .
than that of cobalticinium that in this
to the metal
were
of the cobalt
aton
was important 254. The nitrile
heterogeneous_electron
interface
dicarbollide
for cobaltocene,
analogues
a.c.
polarography.
with
the molecular
Laveron
and Dabard
The rate
Q 0
have investigated oxidation
9
I \
correlated Hurr,
the -chemical (02, or
of the cobalt
complexes
In eac!l case the cobalt-with aqueous
(14.2) 256 .
acid
l,ll-Ciethyl-
a1
Ql0
co
6 0
14.2
pF6R2 14.3
R2
cobalticinium
cation
to a mixture
and the diacid agent
were
using
+
0 in acid
kinetically
obtained
The oxidation
in the complex
cc
E
and their
of the complexes 2%.
structures
iciniurl ion vias obtained. first order
nickelocene
constants
it1 = g2 = ii,Xe, C02We).
(14.2;
at a mercury-aceto-
has been investigated
ii") and electrochemical
was
transfer
with
of the diketone
(14-3;
nas a nitric
References*.288
was oxidized
potassium
(14.3;
X1 = R2 = CO,ii>.
acid-potassium
perman&anste
ii' =.R2 = CO&)
'::henthe oxi6izing
p-ermanganate mixture
then
-m
.-
-.
the &ed_ac&l. was
rpcp2co-
by
(14.3;
salt
formed _- in _ addit%on_to Geiger
.
carboxy
the
electrochenical
ion in dimethbxyethane.
first metallocena
reduction
The anion
was stable
ethane molten
l.,l*-bis(carbethoxy)cobalticiniuz
equimolar
amounts
methyl)benzene
gave
poly(cobalticinium-l,I';
decomposition
salts
occurred
hexafluorophosphate)
hexafluorophosphate)
ivere made to prepare
cobalticiniumdiamine
of
f-diylcarbonyloxymethylene-l,l+-
-ghenylenemethyleneoxycarbonyl Attempts
The reaction
and l,k-bis(hyciroxy-
-diylca$oonyloxydecamethyleneoxycarbonyl and poly(cobalticinium-1,l
in dimethoxy-
hexafluorophosphate
of l,lO-decanediol
the polyesters
anion,
of then cobalticinium
but deco.mposed in acetonitrile 2.58.
with
Rz = CO@
two products 57.
previous
the
ha.4 generated
RX = COXe,
respectively.
polyaLn.ides from l,l'-dicar*~oxy-
by melt
and sure
techniques
.
but extensive
,;olgamides could not be
isolated258j.
15.
cobalt-carbon
Cluster
i4ethylidynetrFcobalt important
Frodusts
Com;>or>nds nonocnrbonyl
from the reactions
and chlorosilanes. 4 de;;endcnt on solvent basicity,
kiaCo(CO)
and the cobalt and cobalt
carbonyl
carbonyl
The
derivatives of cobalt
course
the nature
species.
yxerd thz.
carbcnyl
of the reaction
or was
of the chlorosilane
-Thus silicon
tetrachloride
or lTaCo(CO)k in L'HF or dicthyl
ether gave
Li_d~netrLcobalk
Cl.SiOCCo-(CO>9 259. o<,e-Unsaturated methyl3 3 nonacarbonyl complexes (15.1) viere gregared
by the~reaction
between
the trichloride
vinylic 05
the
trihalomethyl methyl
-yropionic
dicobalt
derivative
derivative
anhydride
cave
(15.1;
octacarbonyl (Scheme
ond the ap;;ronriate
15.1).
ProtonaEon
R ' = ii,R2 = Je) vith
the hexafluoro>hos;hate
iEP?b-
salt of the
281.
BIC!I=C
x2 <+-
3J27-. CO(C0)
ELF
CO$r,O)~
(oG)3co
“X3
Co(C0)
x =
Cl,
3
!3r
15.1
3
Scherle 15.1
carbenium
Treatsent
iozi (15.2).
gave ?SeOCC(We)2CCo3(C0)Q
_
I~?HC(ic~e)2CCo3("0)9260.
of this salt with
and treatnent The
?
M.th
aniline
-cycloheptatriene .
methanol gave-
complex
(15.3) was formed by heating dodecacarbonyltetracobalt and The physical properties of the
cycloheptatriene in hexane.
complex shot:fedsome resenblences to (7-cyclohe>tatriene)The preparation of the cobalt chromiun tricarbonyl 261 o cluster acylium ion (15.4) from carboxymethylidynetricobalt . nonocarbonyi and its esters with sulphurlc acid has been
resorted
with
a~16 ZschSach .
15.4
15.3
15.2
full experimental
details
by Seyferth,
The reacti-zns of th e-acgliu.~ ion
Hallgren
(15.4) M_th
alcohols, phenols, -ti;io?_s,amines, Grignard reagents and organometallic compounds which were oSutlined-in the prgliknary .
References p. 288
-.~
- :;
282
communication 263 have been extended and described in detail 262 . The crystal and molecular structure of tKe mixed crystal q-g-
and g-xylene)enneacarbonyltetracobalt
X-ray analysis.
was’ determined
by
The unit cell data were, space group g2l/g
with a = 10.03: b = 9.86, c = 20.24 8,/3= 96.4O, B = 4.
The
unit cell data for (7,benzene)enneacarbonyltetracobalt viere, space group RJ with a = 9.79 8,
= 82.95O, z = 2.
Both the
structures consisted of a tetrahedral cobalt cluster with
to the arene moiety, while the other
three are each bonded to two terminal and two bridging carbonyl groups.
The aromatic rLngs shoaed no significant distortion
frop local six-fold sywetry 264.
Charge delocalization in
the cluster carbenium ions (15.5;
H = &I, 13e, Ph) has been
investigated by 'E and '3L NX!? spectroscopy.
The results
suggested extensive charge delocalization from carbon to cobalt and compsrisons \'rithferrocenylccarbeniuLqions indicated that the cluster crttions were stabilized at least as effZciently as their ferrocene analogues 265 .
Differences
between tke mass spectra of the conplexad and free tetrahydronaphthalene licand have been observed. CCbRit
The ligand in t:.e
complex (15.6) loses sclal.1 r,eutral molecules (IZ2)with
aromatization Vfhiie atomic hydrogen is lost from the free liEand The results are expktined in terms- of the activation
energies
of possible fragmentation rou tes of the molecular ion266 .
_
283 T'ne reaction of cobalt complexes of the type [YCC_03(CO)J (Y = Cl, Me, Ph), ~(~-CgHs>fjiCo3(CO)~[sCo3(CO)~, and cco~(co)lJ
iwith isocyanides,
(R = Me, But), was
The reactions took place under
studied by Uewaan and Manning. mild
RNC
[SCozFe(CO)J
conditions and up to five carbonyl ligands were displaced
by isocyanide with retention of the XCO~ or SCo2Fe cluster (X = C, Ni, S or Co).
The structures of the products were
discussed 011 the bases of their infrared spectra 267. reduction of the acyl cluster compounds (15.7;
The
R = alkyl or
aryl) to the res:)ective alkyl or aralkyl compounds (15.8;_ R = alkyl or aryl)
was
achieved
under
acid
conditLons,
triethyl-
and trifluoroacetic acid in TIE', yields vaere good
silane
The secondary alcohols (15.9;
(67-?2+).
R = alkyl or aryl)
vere obtained shen t2;e cluster ketones (15-7)
were reduced
with triethylsllsne in boiling benzene folloued by sulphuric ,268 903~ .
acid and hydrolysis, yields varied between 46 and and his co-Trrorkers have continued
Seaferti;
investigations
Arylation
compounds. with
of nethylidynetricobalt
disrylmercurials
Y%? proceeded yields
were
:;hen the reactions
monoxide
irreversible
degradat%on.
aryl groups
hnlogeno-
contrast, References
p_ 288
alkylation
The
ylere carried
material
Zourteen
or
out under
the reversible and
aryl
its
com~~lexes
way in yields of up to 96%.
(Ar) introduced
Introduced,
in benzene
temperature.
were
methox:=-, methyl-,
and a~mlno-;: henyl and perfluoroghenyl.
scroup was also 0
cluster
nonacarbon/l
-;rhichsuppressed
from the starting
(15.10) ‘Nere formed in tWs The
halides
at the reflux
of c.rrrbonmonoxide
loss of cnroon subsequent
and arylmercuric
maxFmised
an atmoqhere
nonacarbonyl
of methylidynetricobalt
in good yield
their
althought
reactions
with
in rather
The
ferrocznyl
low yield.
dialkyluercurials
and
Zy
. ,284
.c&ytiercuric Arylation
halides were slow and gave poor yields of products.
of the
halogen0
cluster
_ Cl, Br, I> with-diphenylmercury structurally
related
compounds
Hal =
(Sill;
The
was also achieved.
acetylenedicobalt
hexacarbonyl
cluster
)3
3
(OC
COGI 15.10
15.9 compound
was
the mono-
phenylated
(15.12)
-:G_thdiphenylmercury
and di-aryl
(15.13)
aechnnisms
for these arylations
(ccric salts)
and thermal
carbonyltriccbalt the acetylenes uere
16
I
formed
radical
and ionic Oxidative
of th= methylidynenona-
IKCO~(CO)~
(I? = Ph, CE2Ph)
It was thought
by the coupling
in yields
were discussed 269_
degradation
compounds
IKE.SH.
derivatives
Alternative
of 21% and lO$ respectively.
to give both
gave
that these acetylenes fragments 270 .
of the tzo methinyl
07-c;i-i5~& Sarnr-tt has reviened
survey
vf.asdivided
oundin;,
into the
ring-addition,
reacticns _
of 19?327!-. nickeloccne disarboxylate
the chemistry
ring
LYhe literature
following cleavage survey
of nickelocene.
sections: and
structure
finally
was complete
The
ligand
transfer
up to the end
Undergraduate experiments for tke preparation and the reaction
of nickelocene
have been described
The reduction
of
with
lithium
of
dimethylacetylene
272 . b:r i3arnett-
(7-S5--5 77)I$ilJCwith
and
alumioiun
285
hydride-alu:r.iniunchloride gave paramagnetic and some nickelocene.
The structure of
[(~-C5-Y5)IJi]4H3
'[(ll_c,H5)Ni] 4H3
was shown to consist of a slightly distorted IJi tetrahedron The hydrogen atoms lay over 7-C5H5 groups at the apices. 273 three tetrrhedron faces . The X-ray structure analysis of
with
the trxple-decker sandwich complex (16.1) h&s confirmed the previous proI;osals based on other evidence,
The three
ligands and tzo nickel atoms are colinear with staggered cyclopentadienyl rinss.
The average nickel-carbon distances
for the two terminal rings are 2.99 and 2.08 2 and for the bridging ring are 2.13 and 2.16 8.
These bond distances are
consistent with the substitution patterns of the complex (16.11 with Lewis bases274.
Court and ii'err:er have presented 'H NKiR Ph
Sal
PII
evidence to support an ionic mechsnis:::for the formation of the triple decker sandvrzch (16.4) from nickelocene.
A solution
of nickelocere in anhydrous hydrogen fluoride contained the ring-protonated catLon (16.2).
Addition of boron trifluoride
to the solution gave the cation (16.3), isolated as the bro:'ln tetrafluoroborate.
The ion (16.3) attacked a further
molecule of nickelocene to form the triple-decker complex (16.4).
Although this route to the product-was favoured by
the authors, the alternative route through attack of the diene conplex (16.2) on nickelocene was not excluded275. References
p_ 288
266
BF4-
Ki
0
6
16.1
The cationic complex (16.5) was converted to the neutral olefin complex (16.6) on treatment with methoxide ion in methanol.
Abstraction of methanol from this product gave
the 3-ally1 compound (16.7).
The 1H iWR spectra of these
complexes y;ere discussed with particular reference to their stereochemistry 276.
The reaction between nickelocene and
dimsthylketene has been reinvestigated by Young.
The orange
solid obtained by miring the reactants in benzene was first assi,'ned an-complexeci lactone structure by SatG, Ichibori znd Satoz78.
It has now been reassigned as the structure (16.8)
16.3
.
16.4 -.
. _--_._ .
__
_-
__ --
287 formed by cycloaddition of one ketene molecule to a cyclopentadienyl ring; of nickelocene followed by insertion of a second ketene molecule into a nickel-carbon bond 277.. The reaction of nickeloceJle v.4th PBu3 or Ph2PBu in hexane gave the complexes h'i(PBu3)4 and Ni(PPh2Bu)Lc respectively.
A similar reaction rlithRPBu2 (R = Ph, E-tolyl)
gave the complexes (7-C5H5)Ri(RpB~2)227g. combined with Ph2PCS-t-Bu nickel complex (16.9).
Xickelocene
to give the 3-cyclopentadienylThe tertiary phosphorus atom in this
molecule was shown to be uncoortiinated, by quaternization ivith Rickelocene was attacked methyl iodide and ethyl bromide 280 .
+ 1 iii
0
@
Ri
by
K_ I -:.
-I-IeO!!
111
I 0
0
16.5
4
ONe Obie'
A-
*
16.6
bis(trifluoromethyl)diazomethane
16.7
to give a 1:2 adduct
with a nickel-cyclopentadiene bridge (16.10)~'~.
.
The kinetics of llgand exchange between nickclocene and (a) lithium cyclopcntadienide (XC +=.)a (b) the tetramethylethyleneciianine adduct of LiC5D, and (c) bis(v-cyclopentadienyl)/ manganese , have been studied, For reaction (a) the rate law suggested that exchange proceeded by two paths.
The first
path involved rate determining association of nickelocene and LiC5D5 and. the second involved similar association of Referencesp.288
.
dimer was forty
time_s as reactzve
formed
a clathrate
did not when
it-accompanied
stabilized
with a th$n
thiourea
All
ferrocene,
degradation
o_f nickelocene
costfng
but nickelocene
attempts
3.
were unsuccessful2' against
rkadfly
Ho_wever nickeloc;ene aas -included
form such a complex.
*with ruthenocene were
with
least
Ferrocene
as the nonomer2'c.
complex
at
form clathrates
Polypropylene
by ultraviolet which
behaved
films
radiation as an energy
agent 284.
transfer
16.10
16.9
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ZIIX?11. ii. ;!iles, Can. Pat.
.
ORGANIC R?ZACTIOZ3 OF SEL?ZCTED~COMPLMES ANNUAL SURVEY COVERING THE YEAR 197%
BERNARD
W. ROCKETT
Department
and GECRGE
of Physical
MARR
Sciences,
The Polytechnic
Wolverhampt on, WV1 1LY (Great Britain)
CONTENTS 198
1. Review6 2. General
199
Results
3.. (')-C5H5)2Ti
202
4. (q-C6H6)Cr(CO)3
203
(i) Formation
203
(ii) Spectroscopic (iii) General
and Physico-chemical
Studies
206 213
Chemistry
217
(iv) Analogues
220
5. (pC6H6)2Cr 6. ~p%p7)Cr(CO13~*,
224
<7-C7H8)Cr(CO>3
228
7. opC5H5MC0)3
228
(i) Formation (ii) Spectroscopic (iii) General
and Physico-chemical
-230
Studies
231
Chemistry
237
(iv) Analogues
8, (Acyclic-7-diene)Fe(CO)3
and ~(7-trimethylenemethane)Fe(CO)3
complexes
238 247
g* q-C&B$"e(cQ)g 10.
(Cyclic-r)-diene)Fe(CO)z_Complexes / @_) Formation QQ
Spectroscopic
(iii) General
and Physico-chemical
Chemistry
254
Studies
1
254 .261 _
198 11.
(~-C+$FeQ-C6H6)
272
l-2.
(py~>p
274
13.
(1'C4H4,Co+C5H9
275
CO ad 14. (7-C5Htz,12
13. Cobalt-carbon 16.
278
[Q-c~H~)~coJ+ Cluster
280
Compounds
284
288
References
1. R.EvIEwS The general
development
has been discussed of titanium,
by Zeppezauerl,
vanadium
di+benzene)
of=-organometallic
and chromium
discussed 2 .
have been
complexes
was also reviewed 3 .
chemistry
of q-cyclopentadienyl,
7Gcomplexes Nobel-prize
4.
Fischer
by Braterman'.
by Knox',
carbonyls,
on the rearrangement
research
work
those
of isotopic
analysis 10 . was discussed
metal
chemistry
metal
complexes
has reviewed
has
the effect
of iron and molybdenum,
of transition
ligands
have been
and in particular
transition
of bicycle k.n.O]
and c-bonded
has been
of transition
Degsnello
of the
has been reviewed5.
complexes
chemistry
especially
of complexes
the
1)-arene and related
review
The organic
been summarized
of 7Gcomplexes
in other sandwich
has discussed
and Wilkinson
substitution inZ-hydrocarbon
possibility
Mawby
7GOrganometallic
included in a more general
spectrometry
Bonding
of hydrocarbon-metal%-complexes
by Bennettbe
cacceptor
and properties
his(r)-cyclopentadienyl),
The7Gorganometallic
winners
The chemistry
of metal
The bonding
and 7-cycloheptatrienyl-q-cyclopentadienyl
compounds
surveyed
chemistry
trienes 9 . metals
The mass
with-aromatic,
has been reviewed. of the elements
The
in the form
199
2. GENERAI;HES&TS Anderson
has used wideline IH NMH spectroscopy to
examine the~structure and bonding in several q-benzene; q-cyclopentadienyl'and 3-cyclooctatetraene sandwich compounds ('2.1; M = V, n_ = 0; M=
Co, n = 1,2;
M = Cr, n = 1;
M = Ni, n = 2;
M = Fe, n = I, 2;
2.2;
_
M = V, Cr, Fe, Co, Ni;
The spectra of the solid complexes were obtained in
2.3).
the temperature range 178-381°K, the second moments of the linewidths were determined and compared with the values using the Van Vleck model. agreement
with very
prillCipa1
molecular symmetry axes.
were
probably
low energy
present
in the q-benzene
compounds
The results were in
barriers
in uranocene
to rotatiori about
(2.3).
(2.1) was
Metal-r%ng
bonding
found to be essentially compounds
(2.2)11.
0 0
32 37.
0
0
u
M
0
0
2.1
2.2 ions
the
Two distinct rotomers
the same as in the 7-cyclopentadienyl
The principal
calculated
formed
2.3
in the mass
spectrometic
frag-
mentation of the 7-cyclopentadienyl complexes (2.2;
M = V,
Cr, Fe and Ni) were confirmed as the molecular ion (7-C5H5)2M+, the 3-cyclopentadienylmetal M+.
The average
ion
dissociation
(7-CsH5)M* energies
and the metal
were
determined
91, 69, 72 and 69 kcal mol-' for the complexes I2 . Cr, Fe and Ni) respectively Referencesp.288
(2.2;
ion as
M = V,
200
Metallation complexes
of the 7-cyclopentadienyl-3-cycloheptadienyl
M = Ti) is lithiated
(2.4; ring
(95%) rather
contrast
metallation
relative
of the vanadium
reactivities
the order M = Ti> used
seven-membered
of these
three
(5%).
ring
and chromium
in the five-membered compounds
A qualitative
V > Cr.
the results 1324.
to rationalize
compound
predominantlyinthe
than in the five-membered
M = V, Cr) occurred
(2.4;
The titanium
(2.4) has been studied.
By
compounds The
ring. decreased
MO approach
in
was
In a definitive
paper,
Q 0
_&I
6
Warren
0
2.4
has discussed
and bis-arene
complexes
configurations
Cmy
elements
state manifolds dependence
and the magnetic
with
the experimental
author
has calculated
static
repulsion
Tanabe-Sugano
moment
results
These
of (7-C5H5>2M,
in the ground
The temperature
auisotropies
for these
in COO*
have also
have been
compared
complexes 15 .
G4 strong-field symmetry
The same
electro-
and evaluated
have been used where
on the
interactionsaud
operators
parameters
the complete
matrices
diagram.
state
Zeeman
The calculated
evaluated.
the ground
for-the
are discussed
Spin-orbital
symmetry.
Possible
field model.
have been calculated.
been
of metallocenes
with &l, a2, _d4 , fi5, s7 and gg
for each &" configuration
of axial
the matrix
behaviour
by use of a ligand
ground-states basis
the magnetic
to
the
deduce
M = V, Cr, Fe, Co, Ni.
202 yield from the oxidation-sensitive complex tricarbonyl(7-cyclohexadienylphenylamine)iron which indicated the mildness of this reaction19.
A US Army report by Rosenblum on
organometallic chemistry covered several related organo-iron chemistry.
areas of
Much of the work in this
report has
already been published by the author in the scientific literature" .
The IR absorption frequencies have been determined for the CO2 groups in a number of mono- and bis-(7=cyclopentadienyl)titanium acetates with increasing numbers of methyl groups on the (q-cyc'lopentadienyl) ligands and with either CF3 or CH3 groups on the acetate ligand21. (3.1;
R = CHMe2,
Treatment of the racemates
CHPh2) with optically active mandelic acid
in benzene led to stereospecific degradation and the isolation of optically active starting material. carried out also with complexes (3.2; C6H3.-2,6-Me2)
bearing
3.1
Teuben
derivatives
R = C6H3.:34fe-6-CRMe2,
cyclopentadienyl
3.2
has investigated
titanocene
a chiral
The reaction was
the thermal
substituent22.
3.3
decomposition
of the
(r)-C5H5)2TiR and their nitrogen
203 complexes
LQ-c~H$~T~R]N~.
The free titanocene derivatives
lost RH by.an intermolecular mechanism:
2(rpC5H&TiR~W
Ti-R
->
%OHgTi
0
d
The compounds showed wide variations in thermal stability dependent on the R group in the sequence: Phe
r=-, R-MeC6H4 < CH2Ph . < "MeC6H4B
The complexes
C6Hs
[(q-C5H5)2TiR]N2 lost nitrogen with the
formation of (7'C5H5)2TiR in the order: R = o_MeC6H4 < C6F5 < CH2Ph < Phm
=-, ~_C6H42~
The green dimeric form of titanocene has been shown by 1% NMR spectroscopy to be a fulvalene dihydrido complex (3.3)24.
4.
(i) Formation (I)-CflHr)Cr(CO "U Rausch has reported an improved synthesis of (q-benzene)-
chromium tricarbonyl.
Equimolar amounts of benzene and
2-picoline containing hexacarbonylchromium were heated under reflux to give a good yield (91%) of the product 25 .
The
reaction of benzocycloheptatriene with chromium carbonyl gave the chromium tricarbonyl complex (4.1) with the six membered The acids PhCH(CHMe2)ring?+bonded to the chromium 26 . CH2CH2C02H and PhCH2CH(CHMe2)CH2C02H were cyclized to give the corresponding tetralones and these-were treated with chromium carbonyl References
p_ 288
to give the complexes (4.2;
R =o<-Me$H,
-2
w$ 4.3
4.2
4.1
chromium tricarbonyl derivatives (4.4;
n = 1 and 2) were
prepared by cyclization of the corresponding propanoic and f o+tetralone ando<-indanone butauoic acids or by reaction 0, with chromium carbonyl28 . The reaction of hexacarbonylchromium with benzocycloheptatriene gave (v-benzocycloheptatriene)chromium tricarbonyl Heating ~-C6Hq[CH(ORt)J2
(4.5j29.
cia 0
.
&,
Ii1
\
w&
0
with chromium carbonyl
/
0 @
_ dr
(CO)
3 4.6
4.5
4.4 gave the complex c4.6;
Rl = R2 = CH(OE~~)] which on hydrolysis
gave the corresponding dialdehyde (4.6; the ether (4.7).
R1 5 R2 = CHO) and
Reaction of the dialdehyde-with ketones gave
the corresponding tropones (4.8)30.
King and Nainan have
205
4.9
4.8
4-7
described the formation of the binuclear anions (4.9;
M = Cr,
W) from sodium tetraphenylborate and chromium or tungsten
hexacarbonyl in boiling diglyme,
The anions were isolated as
their tetramethylammonium salts3?
Neuse and Yannakou have
reported the preparation of chromium tricarbonyl complexes of N-benzylidenear&lLne with metal carbonyl residues attached to either one or the other of the two benzene rings, or to both rings32. syn-(TiDibenaobicyclo[2.2.2]octatriene)tricarbonylchromium (4.11) \vas prepared‘from the arene (4.10) and triacetonitriletricabonylchromium.
Catalytic deuteration
of the complex (4.11) over palladium on charcoal gave predominantly a deuterated product (4.12) with both the deuteriums on the ethane bridge anti to the tricarbonylchromium moiety.
It was thought that this mode of addition occurred
because the tricarbonylchromium moiety served as a blocking group to shield one face of the c&bon
4.19 References p_ 288
->.ll
to carbon double bond33.
4.12
206
Triaqinetricarbonylchromium
was
tre,?ted
with
thiOphC?lle,
t-butylbenzene, phenyltrimethylsilane and iodobenzeno to give the corresponding (T-arene)tricarbonylchromium complexes in yields, as good as or better than, similar reactions with hexacarbonylchromium.
The use of (NH3)3Cr(CO)3 was preferred
in these reactions in that it did not sublime and it VIES more reactive in solution than the hexacarbonyl 34.
(tj-Arene)-
tricarbonylnolybdenum BrXo(CO)- [Ar = PhMe, mesitylene, 5 PhBu, tetralin, (pXe3C)2C6H4, PhO;ie, PhCIkCH2, PhCH2CZ2Cti=CH2, PhC;IgX2CH2Br,
PhCH2CIi20Me,
PhCE2CH2COi3e,
Z,lk,6-i-~e3C6~2CO>~e]
tricarbonyltris(pyridine)nolybdenum
were prepared by treatin
with the aryl compound in ether containing boron trifluoride at 20° 35.
The compounds
benzene, R = Et;
arene
[(q-arene)Xo(PR$d(arene
= mesitylene,
5
R = Xe) were pre>?ared
by reaction of vv -arene)IIo(?-C3H5)Cl~2 with %R3 followed by excess PR3 and NaSH4.
The arene-molybdenum derivatives .:ere
protonated by dilate aqueous acid to give r(rl_arene)~Io(PR3)~H]+ and diprotonated by concentrated acid to &ive [(v-arene)Ko-
4.13
4.14
(ii) Structural an< physico-chemical studies In a theoretical study of benchrotrene, the complete
207
electric carbon This
dipole moment matrix was evaluated on-the metal,
.
centres employing an atomic orbital basis 37.
and oxygen
study was followed by one on (~-c~H~N%)c~(co)~
and
(7-C6H5F)Cr(CO)3 which allowed comparisons to be made of molecular orbitals derived from several approximation methods in common use.
The empirical.method of Basch, Viste and Gray
gave the best values38.
The molecular structure of the benzoic
acid complex (4.13) was determined from three-dimensional X-ray data. p21/s
with
The crystals
w&e
monoclinic,
space
group
unit cell dimensions a = 12.23, b = 7.51, c = 18.1 2
and p= 117.9.
The molecule
(4.13) adopted a conformation
which departed from perfect staggering by about seven degrees 39. Three
dimensional X-ray structure analysis has confirmed the
bis(diphenylarsino)methane adduct of
ctiromi~m
the bridged benchrotrene complex (4.14)40.
hexacarbonyl a6 Meyer has described
the synthesis of several aldehyde, ketone, ketovinyl and hydroalkyl derivatives of benchrotrene by either direct reaction between the ligand and chromium hexacarbonyl or by secondary reactions of substituted benchrotrenes.
The electron with-
drawing character of the chrotium tricarbonyl group was demonstrated by polarography of acylbenchrotrenes, the Hammettsubstituent constant was determined as C=
0.74.. Some aromatic and
organometallic groups were arranged in order of electron withdrawing power;
benchrotrenyl> 2_thienyl>cymantrenyl
)phenyl>2-pyrrolyl>ferroceny141. The rate of hydrogen-deuterium exchange in (CO),PPh3 was directly medium
proportional
at go + 1 to -2.5;
was inverse 4% determined Referencesp_ 288
(7-C6H6)Cr
to the acidity
of the
at 20 -2.5 to -7.1 the proportion
Hydrogen-deuterium exchange rates :rere
for a series
of substituted
arene-chromium
complexes,
'208
(v-RC6H5>Cr(C0>2PPh3(R = H, MeCO, Me02C), (rl-C6H6)Cr(CO)3 and $+Me2NG6H5>Cr(CO)3.
The acetyl and the protonated dimethyl-
amino groups accelerated the rate of exchange43.
The rates
of deuterium and tritium exchange between (?-benaene)dicarbonyl(triphenylphosphine)chromium, labelled in the benzene ligand tithdeuterium
and tritium in CF CO H were determined. No 3 2 isotope effect wss observed and it was suggested that the rate determining step in the exchange might be the transfer of H+ from chromium to the benzene ligand44.
Substituent effects.
in benchrotrene derivates have been studied. by measurement of rates of cleavage for C-MR
3
groups bound to theq-benzene
The triethylgermane (4.15;
ligand.
X = H) was cleaved by
aqueous-methanolic alkali sixteen times faster than the free ligand which gave a value for the Cr(COj3 substituent constant 6=
+0.84.
(4.15;
The relative rates of cleavage fck the complexes
X = m-CF3, @?l,
g- and R-OMe, o- and S-Me, H) were
found to correlate well with the relative rates for the free ligands although the substituents (X) had a smaller effect in the complexes (4.15) than in the uncomplexed arenes.
Similar
effects were observed in the basic cleavage of the aryl-SiMe
3
bond in a series of six silylbenchrotrene compounds (4.16; X = m-Cl, _- and &-OMe, ;- and &-Me, H).
The 6- constant
was determined as +l.l2 for the Cr(C0) group in the silicon. 3 complex (4.17)45.
4.15
4.16
4.17
209
Ceccon and Catelani have compared the rates and products of elimination from the substituted benchrotrenes (4.18; Rl = H, N02, R2 = H, Me, X = Br, OTs), with those obtained from the free arenes.
The eliminations were carried out
with ethoxide in ethanol or t-butoxide in t-butanol,
Higher
rates of reaction were observed for the complexes than for the uncomplexed arenes.
The percentage of olefin in the
product mixture when substitution competed with.elimination was greater for the compleired arene while the proportions of the olefin products were independent of complexation 46.
In a related study, the second-order elimination from the complexes (4.18;
R1 = H, R2 = Me, X = Br, OTs and 4.19)
has been compared quantitatively with the same reaction in the free ligands.
The reactions were induced b-y either
tetrabutylammonium chloride or bromide in acetone.
The rate
of dehydrochlorination of 1-phenyl-1-chloropropane wae almost unaffected when it was complexed as (4.19) but the rate and olefin yield from the 1-phenyl-2-propyl derivatives was decreased on formation of the complexes (4.18).
An Ez!c
transition state for the reaction was preferred over the alternative R2H transition state 47. The kinetics of decomposition of several ('I-arene)chromium-tricarbonyl and References p_ 288
-dicarbonyltriphenylphosphine
210
complexes
was-studied
spectrophotometrically
The complexes
conditions. decomposed
faster
decomposed
to give benzene
rapid-exchange
between
releasing) terms
the conformers
(4.20;
with a decrease
of an increased
The opposite
(R is electron
rotation
shift
for (4.20;
to rotatiM
xH2,
:C=CH2,
kcal
nol'l
at 14-22O
had energy
barriers
respectively.
2, 4
in
(4.21).
c4.20;
R =
tricarbodyl
EIindered compounds
The energy
in the complexes
barriers (4.22;
4.21
4.20
X =
rings
atoms
R = COMeI
(4.20)4g.
by 'H NMR spectroscopy.
of the uncomplexed
by variable
and this was attributed
conformer
in (v-diarylmethane)chromium
for
(R is electron
from conformer
occurred
The
was interpreted
For the complex
of a single
has been studied
118’
in temperature
withdrawing).
to the existence
for carbon
R = Me, Et, OMe)
was observed
C(Me13] no significant
48 .
was studied
shift
contribution
behaviour
Benchrotrene
(4.20 and 4.21)
complexes
An upfield
and 6 in the complexes
compounds.
and- hexacarbonylchromium
benchrotrene
13C ?&R.
first order
triphenylphosphine
than the tricarbonyl
some substituted temperature
containing
under
>CHOH) while
fell in the range the complexes
of 19.4 and The
13.9-14.3
(4.23;
R = H, Me)
19.6 kcal mol-' at 115 and
high barriers
for the ketones
(4.23)
.
211 were ascribed to stabilisation of the ground-state conformations by carbonyl-uncomplexed ring.conjugation5'.
4.22
Bodner and Todd
4.23
4.24
have used Fourier-transform 13 C NMR spectroscopy to study substituent benzene6
effects
were
benchrotrene
when benzene
complexed derivatives
C02Me, NH2, NMe2).
with
and eight substituted
chromium
(4.24;
carbonyl
to give
the
R = F, Cl, Me, OMe, OHun,
No significant
change
in the transmission
of resonance substituent effects was observed between the free and complexed ligands.
The chromium tricerbonyl residue
was effective in withdrawing electron density from the &skeleton
of the erene ring51.
Complete assignments of the vibrational spectra of the benchrotrenes (4.24;
R = NH2, OMe, C02Me) have been made
on the basis of Raman polarization_ results.
The need to
use full factor-group analysis iS emphasised and attention is called to the failure of the 'local' symmetry concept which has been used previously 52.
A single-crystal Raman
study was made of the vibrations of-the tricarbonylchromium unit in benchrotrene and tricarbonyl(l,g-dimethylbenzene)chromium.
In the 2000 cm"
wa6 appropriate.
were interpreteds3.
region a factor group analysis
Also, low frequency bands, 400-700 cm-l,
.
-212
The chemical ionization mass spectra for the (T-arene)chromium tricarbonyls (4.24i
R = H, Me, F, Cl9 GO,Ple> have
been recorded and compared with the spectrum of q-cycloheptatriene)chromium tricarbonyl..
In each case the spectra
were interpreted in terms of protonation at the metal atom. In the case-of di(q-benzene)chromium the most abundant ion was the molecular ion formed by loss of a hydrogen atom from the protonated complex54,
The dissociation and fragmentation
of six alkyl- and halogeno-benchrotrenes has been examined by mass spectrometry,
Appearance potentials were measured and
dissociation energies obtained for the neutral molecular and the major fragment ions 55.
The mass spectra of (v-acetanilide)-
tricarbonylchromium and the 2,4- and 2,6-dimethyl analogues indicated that ketene elimination from the ion ~C6R5RHCOCH3)C~+ . occurred via a six membered transition state, Scheme 4.1 5%
Scheme 4.1
In the mass spectrometer (y-methyjbenzoate)tricarbonylchromium underwent secondary electron capture to give a molecular ion which suffered decarbonylation and further loss of three CO groups.
Cr- ions were also identified in the 7OeV negative
ion mass spectrum of this compound 57.
The use of mass
spectroscopy for the analysis of mixtures of (q-benzene)tricarbonylchromium complexes was investigated,
Intense
213
peaks were obtained for the molecular ions [(7-CgH5X)Cr(CO>d+ (X = 11,Me,.Et,
F and Cl) and r(t?-C6H5X)Cr]+.
[(~-c~H~x)c~co]+B~-c~H~x)c~(co)~]+ useful
The ions
and (c~H~x)+ were
also
in the identification of the (q-benzene)tricarbonyl-
chromium derivativess8.
(iii) General Chemistry. Benchrotrene was mercurated with mercury (II) acetate to give the derivative (4.25;
R = H) in 29% yield.
Triethyl-
silylbenchrotrene was metallated in the same way to form the disubstituted compound (4.25;
R = SiRt3)59.
The quantum
yield for the photochemical decomposition of benchrotrene . in cyclohexane was found to be proportional to the rate constant for decomposition and was inversely related to the intensity of the light used.
A
complex mechanism of
decomposition was indicated with three competing reactions 60 . Jaouen and Dabard have cyclized the butyric acid (4.26).with polyphosphoric acid to give a mixture of the endo-cyclopentenone (4.27),
52%
and the e-isomer
(_4.28),48%.
When either the
endo- or the exo-isomer was heated with sodium methoxide then an equilibrium mixture of the two isomers was obtained containing the same proportions as were
formed in the initial cyclization,
The equilibration presumably proceeded through the enol form (4.29) of the cyclopentenones.
Cyclization of the butyric acid (4.30) also gave a.pair of isomeric products 61 o
R\
P0
HgOAc
(%, 4.25
4.26
4.27
4i28
4.30
1.29
The reac_tion of methylmagnesium iodide with the dialdehyde (4.6; R1 = R2 = CHO) gave a mixture of two meso, pseudoasymmetric glycols and one racemic glycol
r4.6; R1 = Rz = CH(OH)Me]. ligands
Photochemical removal of the
gave two diastereoisomeric alcohols (4.31).
Oxidation of the alcohol_ c4.6; R1 = CH20H, R2 = CH(OH)Me] gave the cyclic hemiacetal (4.3Z; X = H, R = OH) and the phthalide (4.32;. X = 0, R = H)62.
The Penchrotrene monomer
CH(OH)Xe
4.32
4.31
(4.33) was prepared from (q-2-phenyIethanol)chromium tricarbonyl and acryloyl chloride in benzene.
Approximate reactivity
ratios were obtained for the copolymerizatfon of the monomer (4.33)mwith styrene, methyl acrylate, acrylonitrile and 2-phenylethylacrylate in ethyl acetate with azobisisobutyronitrile as the initiator. (4.34;
High yields of the copolymers
R = Ph, C02Me, CN, C02CH2CH2Ph) were obtained at 70°
and
all exhibited
The
organometallic
bimodal
molecular
residues
weight
decomposed
distributions.
in sunlight
and on W
irradiation in air or under nitrogen with the.initial-formation of Cr203 63 . The symmetrical benchrotrenyl mercury compounds
(~HCi12cHRcH2)n
Q-
cHpi20coH=cH2
CH2CH,0C0
0
4.33 R = H, Me, OMe, NMe2)
(4.35;
aluminium
hydride
to give
Cleavage
cleaqed
the substituted
with iodine
(4.36;
at low temperature
R? = H, Me, OMe, NMe2,
with
lithium
benchrotrenes
(fj-Chlorobenzene)chromium the anion
in ether
activating References p-
tricarbonyl
of isobutyronitrile
(4.39;
complex
288
gave
the iodo-benchro-
R2 = I> 64.
4-36
4.35
iodine
were
Rl = H, Me, OMe, Nt4e2, R2 = H) in good yield.
(4.36;
trenes
4.34
(4.37)
treated
to give the chromium
R = CMe,CIJ) which was readily to give phenylisobutyronitrile.
effect
was
of the chromium
tricarbonyl
with
tricarbonyl
cleaved
with
The large was apparent
-
216
-in that the reaction wae complete within 20h whilst no reaction occurred with uncompl&xed chlorobenzene over a Several other anions were-used successfully
similar period.
in this reactidn, however those generated~from 1;3-dithisne, 2-methyl-1,3-dithisne, tert-butyl acetate, acetophenone, 5,6-dihydro-2,4,4,6-tetramethyl-4EJ-l,3-oxazine and acetonitrile fai.led63.
The mechanism of the reaction of carbauions with
(v-chlorobenzene)chromium tricarbonyl (4.37) was investigated. It was suggested that attack by the carbanion occurred to form a (rj-alkylcyclohexadienyl)chromium tricarbonyl anion (4.38) followed by irreversible loss of halide anion to give the When an electrophile was added to the reaction
product (4.39).
system of-(4.37) and the anion, followed immediately by addition chlorobenzene,
of iodine, the following products were isolated;
phenylisobutyronitrile, g- and g-chlorc(2-cyano-2-propyl)benzene and a series of dihydro analogues of these last t7;o products66,
+
?&-
‘$If
0
+
cl-
Cr (cJO13
4.37
4.38
4.39
(7-Mesitylene)chromium tricarbonyl and other (q-arene)chromium or molybdenum tricarbonyls have found application as catalysts for the polymerization of phenylacetylene 6? (q-Phenanthrene)chromium tricarbonyl-has been.used to catalyse the selective hydrogenation of a propellatetraene to-the
217
corresponding propelladiene 6% .
Phenylacetylene-was polymerized
rapidly and quantitatively in the presence of (q-toluene)molybdenum tricarbonyl to give linear polymers with molecular weights up to 12,000.
The polymerization proceeded'via a.
ladder polymer intermediate which wae isolated when (7-mesitylene)chromium tricarbonyl was used a6 the catalyst. The ladder polymer rapidly gave linear polyphenylacetylene in the presence of (tj-tolueneholybdenum tricarbonyl and this reaction was thought to proceed via a free-radical mechanism 69 .
(iv) Analogues Jaouen and Dabard have ccnverted monosubstituted benchrotrenes into chiral complexes by replacement-of carbonyl groups by other ligands.
Thus (v-methylbenzoate)chromium tricarbonyl
was treated irith cyclooctene to form the derivative (4.40; L = C8H14) and this intermediate wa6 stirred with carbon disulphide and triphenylphosphine to give the thiocarbonyl complex (4.40;
L = CS).
Irradiation of the thiocarbonyl
complex with triethyl phosphite led to the chiral phosphite Several disubstituted benchrotrene derivative6
(4.41). c4.42;
X = H, But, Me;
PPh3] were described?',
R = H, Me, menthyl;
I, = CO, P(OR)3,
The photosubstitution of a carbonyl
group in (q-ArH)Cr(CO)3 by N-phenylmaleimide (NPhMI) gave References p_ 288
_
Irradiation of complexes of this'type
Q-ArE)Cr(CO)2(NPhMI).
in the presence of a phosphite gave the chromium complexes (4.43
and 4.44).
These compounds are the -first neutral
asymmetric (90benzene)chromium (0) complexes with the metal atom as the
chiral centre,
The vinylic protons of the
N-phenylmaleimide ligand were diastereotopic and displayed Photolysis of qa temperature dependant 1H NMR spectrum7'.
Q 0
0
Cr C0.P(OMe)3.
4.43
0
iiPh
CO.P(OPh 4 -44
c
0
0
-LCr(CO)3[L = hexamethylbenxene, mesitylene, E-RC6H4Me, (R = Me2N, Me, MeO, F and CO2Me), C6H6, and e-(Me02C)2C6H41 in the presence of 2,3-diazobicyclo[2.2.1~hept-2-ene gave I;I-LCr(C0)2Ll.
(L1)
The ligand Ll was coordinated to
chromiu1r through the lone pair of electrons of one of the nitrogen atoms of the N=M double bond72.
Connelly and
Demedowicz have displaced carbonyl from (7-C6Me6)Cr(CO)3 using the diazonium salts (H-.NCgH4N2>X (H = li,X = FFg; R = OWe and NO 2, X = BF4> to afford the complexes (7'C6Me6)Cr(C0)2(R-RC iIN )fX-wbich were cla?i_ned to be the first 642 examples of arylazochromium derivatives. Treatment of these derivatives :fith sodium borohydride gave the corresponding neutral cyclohexaciienyl complexes (7-r,6~~e6H)Cr(C0)2(E_IiC6H4~i~), The reaction of (r;i-C6ife6)Cr(CO)2PPhg with (H-RQH~N~)+
gave
the paramagnotic cation [r)-C6Me6Cr(CO)2(PPh3)]+ where the diazcnium salt had behaved as an oxidizing agent.
219
(r7-C6Pie6-Ploo(CO)3
was treated also with (o-RC6H4N2)+ to give
complexes that were apparently analogous to~the chromium species but no stable products were isolated 73.
The reaction of
(v-C6Xe6_nHn)Cr(CO)2PhCECPtl,.n = O-and 1, with either I~OP&'6 or AgPF6 gave the air stable salts [(7-C6Ne6;nHn)Cr(CO)2 (PhCZCPh)]pF6.
The carbonyl stretching frequencies for the
cations were 100-15O.cm -' figher than those of the neutral ccmpounds,
Cyclic voltammetry showed that the neutral acetylene
complexes underwent a reversible one-electron oxidation 74. 6-Methyl-2&thiopyra:
iVas heated with (XeCi1')3Gr(C0)3 in
dibutyl ether to form the benchrotrene analogue (4.45)
in which
sulphur coordinates to the m_etal with nonbonding as well as olefinic electrons.
The physical properties of the complex
were compared with those of (t'j-thiophen)ciironium tricarbonyl and the corresponding (q-1,2-dihydropyridine)chcomiun complex75. 3iophen)cbrcmhun tricarbonyl complexes was A series of (7-t.
4045
Scheme 4.2 prepared by reaction of the appropriate heterocycle with (IqeCN)3Cr(CO)3.
The yields
in
these eeactions were higher
than in preparations utilizing Cr(CO)6. Referencesp.288
The separation
and decomposition of the thiophene complexes was studied by gas-liquid chromatography.
Treatment of the complexes with
benzene resulted in ligand exchange (Scheme-4.Z)76.
The
1HLiMR spectra of the q-thiophene complexes were analysed7'. The treatment of (P7-Me3B3N3Meg)Cr(CO)3 with Me3B3N3H3 brought ‘about ligand exchange to give (v-Me3B3N3H3)Cr(CO)378.
scotti
and Werner have attacked substituted borazines with Cr(C0)3(MeCN)3_to give the chromium complexes (7-R13B3N3R23)Cr(CO)3 1 = Pr, R2 = Me; Rl = Me, R2 = Fr; R1 = iso-Pr, R 2 = Me; 2 = Me, R2 These compounds were more labile than the isomeric complex (7-Et3B3N3Et3)Cr(CO)g which was prepared from (7-iX3B3N3Meg)Cr(CO)3 by ring'ligand exchange 79.
The direct synthesis of bis(q-m-diisopropylbenzene)chromium, bis(T-cumenelchromium and (v-biphenyl)(y-g- dipropylbenzene)ChrOmiUm
from
C~0Kh.m
and the arenes has been reported 80 o
Chromium atoms were cocondensed with benzene in an argon matrix, on a caesium iodide window at 14OK, to give di(y-benzene)chromiup which was characterized by infrared spectroscopy 81 . Nickel atoms were treated with hexafluorobenzene to give a highly reactive and explosive complex.
In a similar manner
hexafluorobenzene and benzene were allowed to react with chromium to give presumably bis(hexafluorobenzene)- and di(v-benzene)chromium respectively 82 . The formation of bis(q-arene)metal complexes has been achieved by condensation of metal atoms obtained by resistive heating with the arene at -196'.
Arenes used were benzene, toluene, xylene, anisole
and fluorobenzene and these were condensed with molybdenum and fungsten83.
Bis(v-arene)molybdenum complexes have been
221 separated from mixtures and purified by molecular~distillation 84 . A series of bis( -fluorobenzene)chromium complexes-(q-C6HkFX)#r
7 (X = H, F, Cl, CH3, CF3) were prepared by cocondensing chromium
atoms and fluoroarenes,
The lg F NMR spectra of these complexes
suggested that the overall electron-withdrawing effect of a W-bonded
chromium atom on each ring was similar~to that Of
four ring fluorine substituents 8% The X-ray photoelectron (ESCA) spectra Of fourteen bis(7-arene) and (y-arene)tricarbonyl complexes of Cr, pin and The binding energies
Fe were measured in the solid state. were interpreted with the aid of &
initio SCF MO calculations
for (t7-C6H6)Cr(CO)3 and (3-C6H6)2Cr and semi-empirical MO calculations on most of the other compounds.
In neutral
bis(7-erene)metal complexes the arene ring carried a small negative charge and the electron density on the ring was higher than in the comparable (v-arene)tricarbonyl complex 86 ( Simple mass spectra were obtained, for a series of bis(7-arene)chromium and -molybdenum complexes, at 60o for the chromium compounds and at 100° for the molybdenum compounds, by the use of a field-ionization source.
The ions (5.1;
i+ =
Cr, .pIo)
were formed preferentially and the method was suitable for qualitative and quantitative analysis,
Mass spectrometry
wvith field ionization was also used for studying the thermal - 87. decomposition of these compounds
The dependence of the
hyperfine structure of EPH signals of bis(r/-arene)chromium compounds [e.g. (7-PhH)$r+,
(q-PhMe)$r+,
(I?-PhPh)#r*] on
temperature (-160~-+70~), viscosity, solvent and magnetic field was studied.
The line width temperature dependence was
explained by the relaxation mechanisms: anisotropic Zeeman interaction; References
p_ 388
when o?r >I_, an
vrhen oTt(
1, a modulation
of spin reversalinteraction 88 . ~bisq-arene)chromium.iodides
A synthetic mixture of
was resolved by partition liquid
.chromatography and the chromium content in each fraction was determined by atomic absorption spectrometry 89 .
+
Q 01
0’
0
O-
0
M
Cr
6 0
The kinetics
0
R
& t
I-
0
6-R
5.1
5.2
5.3
of hydrogen-deuterium exchange for the R-= H, Ze, Zt) in L;t@D-EtONa and for the
complexes (5.2; salt (5.3;
Q-
+
R = 11,r.le) in D20-KOD were studied*.
In both
reactions deuteriun e!itered both the aromatic nucleus and the
side chain".
The kinetics for the thermal decomposition
of the diarenc complex (~-PhEt)2Cr was correlated with its field mass spectrum 91.
The saturated vapour pressures for
a series of bis(q-arene)molybdenun complexes were determined and the-heats of evaporation ?lr-recalculated-92 _ The saturated vapour pressures of the benzene complexes (q-Ph!'>2Cr, (7-P&(9-PhEt)Cr
9 (7-PhLt)C7-C6H4Et2)Cr alid (7-C6H3Me3)2 Cr
yiere deternined at 20-110' and the heats of evaporation were 3easuredg3.
z Rxwessions
have been derived to correlate the
physicochemical properties, such as densit;::and vapour pressure, of bFs(q-arene)metal complexes.
The arene ligands :fere benzene
and substituted benzenes and the metals were chroaiu:l, Zmolybdenum and tungsteng4. Bis(r)-bcnzene)c':*roniu!~ ;:as Xeteroann-ularly dilithiated with
223
a mixture of butyllit'hium and TiGDA in cyclohexane at 70'. The lit:hio intermediate vfas stirred with diphenylchlorophosphine to give the diphosphine (5-4) which was coirverted to the dimethiodideg5.
Xixed sandwich complexes of c'hromium have been + 2 AlR2C12
PPh2 Cr
5.4
5.5
formed by direct reaction between chromium salts and acetylenes. Treatment of 2-butyne with chromium (III) chloride and tri. alkylaluminiuts gave the q-benzene cation (5.5; R1 = He, R2 = He, Et, Pr>.
The cation was reduced with lithium
aluminium hydride to the neutral sandwich compound (5.6; R=Me).
. Replacement of 2-butyne with 2-hexqne in the same
reaction gave the y-benzene cation (5.5;
R1 = a,
Rz = LXe,
Et, Pr) which on reduction formed the T-benzene complex (5.6;
R = 53~).
It was suggested that the polyalkylbenzene
ligands vere formed by cyclotrimerization of the acetylenes while the cyclopentadienyl groups arose by cleavage of the acetylenes at the triple bondg6.
Eis(t)-diphenyljchromium
was oxidized with a stream of oxygen in the presence of l,+diphenyltriazine
to give the salt (5.7) which was isolated
as the sesquihydrateg7.
References
p. 288
BisOpethylbenzene)chromium
was
224
5.7
5.6 pyrolysed
at 350-450'
for 10h to give methane,
carbons and chromium as the main products
C2-C4
together
hydro-
with
mink
amounts of hydrogen, toluene and ethylmethylbenzeneg8.
6.
[07-C7H7)Cr(CO) dc, AII improved
(f7-C7H~,)Cr(CO)3
synthesis
04 = Cr, MO) was reported i-C$i5MgEr.
The reactants
TiiF-diethylether
0
at -20 .
for the compounds
(v-C5H5> (r?-C7H7)M
from 19iC13.3THF, C7Ha, were mixed
together
C5H6 and in
The product was purified by
sublimation and subsequent recrystallization.
The synthesis
and properties of (7-C5H5)(T-C7H7):4, (M = !&r,Nb) were reportedgg.
Green and co-workers have reported a general
route for preparing non-carbonyl cycloheptatrienyl molybdenum compounds via the facile displacement of the arene ligand from the complexes
[Q-C75)(7-arene)
Xo]+PF6- as shown in
Scheme 6.11"'. The crystal structure of 1,3,3,5-tetramethyl-6-(1',2*naphtho)bicyclo[3,2,l]octenechromium determined by X-ray analysis.
(0) tricarbonyl was
The crystal data was as
follovEi: space group s2/~, a = 19.66, b f 14.35, c = 16.442, = 120,1°, z = 8.
The cyclohexane ring was distorted from
the normal chair form due to the steric interaction of an
:ioPPh_(acac)
Scheme
6.1
0 naphthalene moiety and the strain axial methyl group with th, of fusion through a five-membered ring to the naphthalene moiety.
The chromium atom was complexed to the ring of the
naphthalene that was fused to the aliphatic part of the moleculel~l.
X-ray photoelectron spectra (ESCA) on
$'-C5h5)(7-C7h7)M, (M = Ti, V, Cr) and some related compounds showed that the oxidation state of the metal increased in the sequence Cr< V< Ti.
This resulted in an-increased electron
density on the ligancis in the same sequence.
In the Cr
compound the cyclopentadienyl ring was more negative than the cycloheptatrienyl ring; References p. 288
for the V compound about equal negative
226
charges were found on the two rings;
while for the Ti compound
the'highest negative charge was found on the-seven membered ring102; 13 C and IH Nk3R spectra of the compounds (7-C5H5)(q-C7H7)X, (W = Ti, Zr; &lo, Cr) were recorded. the chromium compound the 13C reson&e
For
of the ~-C,-& ring
was at lower field than that for the 7-G5H5 ring,
whilst
molybdenum compound the two signals were close together.
fOl?
the
r
It was concluded that the q-CsH5 ring was more negatively charged than-the q-L/$ ring in the chromium compound. 1H NMR spectra indicated hindered rotation of the rings in The mechanism of the chromium and molybdenum compounds 103. fluxional rearrangement in (7-cyclooctatetraene)trice.rbonylmolybdenum was investigated using 13C MR
spectroscopy.
The results ruled out a 1,2 shift and it was proposed that . the rearrangement process involved a symmetrical "piano stool" intermediate (6,1), Scheme 6.2, with the metal atom lying over the centre of a flat octagonally symmetric C8H8 ring 104 .
(co) - x0-
5
;0.--_
I~~o(co)3 \ ..-I\
,-
\
:
\-__* I
0
\
6.1
“__
;
227
The fluxional behaviour of the chromium tricarbonyl derivative (6.2) was reexamined with 13C NXR and it was process occurred.-- For the chromium
proved that a 1,2&hift
tricarbonyl derivative (6-s), 13C NMR showed that 1,2-shifts were not the pathway and that only 1,3-shifts or a process 'resulting in random shifts were admissible 105 _
$I
Q
6.2
.
6.3
The reaction of (v-cgcloheptatriene)metal tricarbonyl (where metal = chromium, molybdenum or tungsten) with acetonit-rile obeyed third-order kinetics.
The reaction was
interpreted in terms of pre-equilibrium association between then-complex
and acetonitrile which was followed by rate-
determining addition of a further molecule of acetonitrile. The ease of displacement of the ligand decreased in the order i+Io>X>Cr. the
COni,oleX
Displacement of the aromatic ligand from
(7-C6H3Me3)i”iO(CO)3
by acetonitrile _ followed
second-order kinetics and led to the following order of displacement of ligands (L) from the complexes LMo(CO)~~+ where n = O,l;
7-C71i8>'7-C6~3"e9>3-C7H7106~
of D'7-c7H7)Mo(C0)~BF4
with triphenylphosphine gave
~~-C7H$';10(CO)2PPh~BF4
nhich was reduced with sodium
borohydride to g~ve'(~-C7H~)&~o(C0)2PPh3107. complexes of
chromiun
The reaction
(6.6; R1 = Ph, He, H;
Yepta-fulvene R2 = Ph, Me, H)
have been obtained from the -l-substituted cycloheptatriene References
p_ 288
compounds (6,4).by hydride ion abstraction with triphenylmethyl ~fluoroborate to form the tropylium salts (6.5) which were treated pith 1,8-bis(dimethylamido)n~phthalene,
a strong
anon-nucleophilic base, to abstract a proton and give the These compounds resembled free heptafulvenes
products (6.6).
in their reactivity towards electrophiles with exclusive attack at the exocyclic double bond 108.
6-4
7. 07-C5H+n(CO)
6.5
y
6.6
(i) Format-
C?-(Trior~anosilyl)cyclopentadienyl]tricarbonyLmanganese compounds were prepared by treating a (triorganosilyl)cyclopentadiene with an alkali metal, heating the resultant metal derivative with manganese (II) salts and treating the intermediate bis(7 -cyclopentadienyl)manganese with carbon monoxide at lOO-200' and 50-200 atmospheres 109_ The dioxolanylcymantrene
(7.1) was _urepared by condensation of
acetylcymantrene with epichlorhydrin in the presence of tin (IV) chloride using carbon tetrachloride as solveni?lO. Bis(cymantreny1) copper silver (7.2) was formed by treatment of cymantrenylsilver vlith copper (I) iodide in benzene. The ccmplex (7.2) -.vasconverted to benzoylcymantrene with benzoylchloride, to~phenylcymantrene with iodobenzene and to
229
ferrocenylcymantrene (7;3) with ferrocenylbromide, . -xields~were in the range 70-i33YP1.
King and Ackermann have investigated
@Ox 0
Cl
XIl
WO13 7.2
7.1
7.3
the reactions of olefins and acetylene with [HMn(CO)4]3 under mild conditions.
Dienylmanganese tricarbonyl compounds
(7.4) were formed in several cases, thus 1,3-cyclohexadiene give the cyclohexadienyl compound (7.4; heptadienyl compound (7.4;
(7.4;
n = 3j
The cyclo-
n = 2) was formed from both
cycloheptatriene and 1,3-cycloheptadiene. with lJ,+cyclooctatriene
n = 1).
The same reaction
gave the cyclooctadienyl compound
together with other manganese complexes.
The
dienyl complex (7.5).was formed in addition to a fluxional dimanganese complex when cyclooctatetraene was the reactant. Xhen
dimethylaminofulvene
derivative (7.6)
7.4
R&?rences p. 288
was
used
then the cymantrene
was obtained112.
7.6
2io ;Sii> Saectrosconic and-Physico-chemical Studies ..&mantrene was irradiated tiith-X-rays.ar electrons -and the free radicals formed were exanined'by
EPR
spectroscopy.
The-anisotropic spectrum of the final, stable paramagnetic species was compared with the theoretical model
based
on-the
crystal field approximation modified for covalency effects 113 . The frequencies of-the metal-cyclopentadienyl and metal-carbonyl stretching modes in $J-cyclopentadienyl)tricarbonyl-manganese and -rhenium were compared,
The frequencies of the manganese-
-ring stretching vibrations increased whilst those of manganese-carbonyl decreased with an increase in%-acceptor properties of the substituent H in the ring.
The frequency
of the rhenium-ring stretching vibrations was independent of the substituent R.
These differences shoned that the
dative d?t(metal)-p&CO) was more important in the formation of the metal-ring bond in (r)-RC5H$!-ln(CO>3than in the corresponding rhenium compounhl14.
Parker has obtained the IR and laser
Raman spectra of cymantrene and (~-C5D5>Iti(CO)3.
The solution
spectra may be assigned approximately on the basis of C _5V 'local' symmetry but this approach cannot be used for the assignment of the solid state spectra 115. the manganese-q-cyclopentadienyl
The protonation of
complexes (7.7 and
studied with 13C and 31P NMH techniques,
7.8) was
The complexes were
subject to rapid reversible protonation at the metal atom in the presence of trifluoroacetic acid.
The protonation was
governed by the basicity of the manganese atom which depended on the number and nature of the phosphine ligands.
The
basicity of the diphosphine complexes (7.8) was higher than that
of the
monophosphine
complexes
(7.7)
and the alkyl-
phosphines were better electron donors than triphenylphosphine 116.
izn C0.L 7.7
L = P(C&&,
P(i-C3H$3, PPh
7.8
IL*= PPh5 Lz = Ph2PCHZCH2PPh2,
P(cH2Ph+
Ph2PCH2CE2CH2PPh2
3
The IH NMH spectra of cymantrene and fifteen monosubstituted cymantrenes have been compared with the spectra of the corresponding rhenium compounds. . In each case the electron density on the 3-cyclopentadienyl group was higher in the cymantrene compounds than in their rhenium analogues 117 o (iii) General Chemistry Treatment of the (v-cyclopentadienyl)manganese complexes (7.9) with hydrogen borofluoride in tetrahydrofuran gave the gold complexes (T-10;
R = CO, PPh3)l18. AuPPh_
5
Tricarbonyl(y-cyclo+
AuPPh_ 5 BFL&-Ilrl
(=$R 7.9
7.10
pentadienyl)manganese was treated with Et2NPC12 to give
&CO)3Mn(7-C5H4)]3P= C13PS and -methyl iodide
Treatment of this phosphine with Hz02, gave [(CO)3Mn(~-C5H4)1~P0, KCO)3-
413
Mn(7-Cg H ) PS and [(CO)3Mn(7-C5H4f13$MeI- respectivelyllg. The photochemical reactions of (~-C5H5)~Mn(CO>3 and (triphos) gave (r)-C5H5)~In(CO),(CS) with (Ph_,PCH2CH2)21?'Ph (7-C5H5)Mn(CO)(triphos), as two isomers (7.11
and 7.12) and
232
(7-C5H5 )Mn(CS)(triphos) respectively,
as two isomers, (7.11 and 7.12)
The presence of one uncoordinated phosphorus
atom in the complexes was confirmed by their-reactions with Cr(CO).$THF) and (7-C5H5)Mn(CO)3 to give the bimetallic species, (7'CgH5)(CO)Mn(triphos)Cr(CC)5, (7-CgH5)(CS)f4n(triphos) Cr(CO)5, (7-C5H,$CO)Hn(triphos)Mn(C0)2~7-C5H5)
and (745H5)
(CS)~Nn(triphos)Mn(C0)2(rl-C5H5). The reaction of (q-C5H5_) Mn(CO),CS with Ph2PCH2CH2PPh2 gave (7-C5H5)YZ(CS)Ph2PCH2CH2PPh2. The absence of any CS substitution by the phosphorus ligands demonstrated the stronger metal-carbon bonding in metal thiocarbonyls as compared to metal carbonyls12',
L =
L 7.11.
co,
GS
R = CiiCB PPh 22 2
7.12
(7-Methylcyclopentadienyl)tricarbonylmanganese
was fed
orally to rats and it caused histopathological changes in the lungs, liver and kidney. to the dose,
The degree of severity vias related
Manganese concentrations in the tissues of the
animals given 15-150 m&/kg was high,.those that survived the treatment had normal manganese levels fourteen days after the complex had been administered. manganese metabolism
The results indicated that
was homeostatically
controlled
and
that the manganese was transported in the tissues as a netabolite of the original complex 121 . The thermal stability of siloxanes containing tricarbonyl(7-cyclopentadienyl)manganese
233
was
reviewedl=,
Acetylcymantrene was converted to the ketal
(7.15) by treatment with epichlorohydrin and tin (IV) chloride in carbon tetrachloride 123.Silvercymantrene was treated with trinitrobenzene and tropyfium tetrafluoroborate to give the
.
anion (7.14) which was oxidized to 1(2,4,6_trinitrophenyl)cymantrene124.
The cymantrene
gold complex (7.15;
7-14
7.13
X = CO)
7.15
was irradiated with triphcnylphosphine ;inbenzene to give the cymantrene analogue (7.15;
X = PPh5).
When an excess of
triphenylphosphine was used in the reaction then gold-carbon cleavage was observed rather than replacement of a second car-bony1 group by triphenylphosphine-125a The effect of manganese based additives, e.g. (7-methylcyclopentadienyl)manganese tricarbonyl on the mass, size distribution and the chemical composition of particulate emissions from gas turbine combustors. was investigated, The presence of large amounts of Q-methylcyclopentadienyl)manganese tricarbonyl increased
the mass of the emissions with
the manganese being discharged as MnO 126 .
Lithiocymantrene
was treated with triphenylsilicon-, triphenylgermanium-, triphenyltin- and triphenylead-chloride to give the cymantrenes
(7.16; M =.Si, Ge, Sn, Pb). in the tin compound (7.16; References
p. 288
The tin-cyclopentadienyl bond H = Sn) was cleaved with dry HCl
~&fetalcarbonyls and orginonetallic compounds, including methylcymantrene, have been incorporated into polymeric an&o&es
of benzyldiphenylphosphine.
The
polymer-bound complexes have been evaluated es hydroformylation and oiefin isomerization catalysts 128_
Xn (CO) 3
7.16 ET-MeC5H4)fi(C0)2NOJ+
i4ll
(CO)2itO
7.17 PF6- was treated with (g)-(+)-
-HePhChN~4e(PPh2) (ligand L) in acetone in the absence of air to give the pair of diastereoisomers of the tetrahedrally The isomers
-coordinated complex
~~-X~C~H~)X~(CO)(NO)LJ+PF~-. were separated by fractional crystallization 129 .
Details
have been given for the preparation of C('/-C5'15)I.I"(CO)2NO]PF6 from (7-C5II5)Mn(CO)3 and ivOPF6130 a (7.17;
The cymantrene analogues
R = H, 14e) gave the carboxamides (7.18;
R1 = H, Me,
R2 = alkyl, aryl) on treatment with primary amines in ether 131 . -AeC H )PIn(C0)2THFwith an excess of Q?54 O<-diazodeoxybenzoin gave the phenylcarbene complex 7.19?32. Reaction of
7.18
7.19
7.20
Treatment
‘of c$ti&trene
the mixed
complexes
writh $ubstitut&d
of the isoelectronic
(~-c~H~)M~(c~)~cH,=cH,
indicated
that
dependence
the ethylene
motion
kcal/mole
ligand
reported133. dienyl
Q 0
hindered
The activation
of LMII(CO)~THE
complexes
(7.24;
with
rotation
barrier
complex AGzz8
= ll.4
analogues has been
(L =v-cyclopentaPhMeCN2
gave
R = H and Me).
the The
R
Mn (CO)2L
expected spectra
carbene were
complexes
obtained
(7-C5Hs)Mn(CO)2L,[L CSHIONH,
were
electron
not isolated 136.
for a series
of complexes
= CS, CO, P(OPh)3, The results
C8H14].
increasing
7.23
7.22
7.21
density
P(OMe)3,
suggested
l3c NXR of the-type PPh3,
metal
CS<~O
was a betterfl-acceptor
of the
PBu3,
that the order
at the transition
of
wasand
than C0137.
(7 -cyclopentadienyl)manganese
. r
was AG&_
complex
7.22 and 7.23)
and 7-methylcyclopentadienyl) imine
-: .
spectra
of the cymantrene
L = cs, cs2;
The reaction
acetophenone
of these
in the manganese
The formation
R = H, Me;
(7.21;
of-21-2&3~,
comp&xes:
underwent
and in the chromium
kcal/mole 134.
gav-e .t
(1-cgH5)C'(Co)(~0)C~~="H2. were
the metal-ol'efin bond axis.
for the ligand
= 8.4
and
The temperature
analysed.
around
R = ii,-acyl) in yields
(?..?a;
The %i NMfi spectra
vinylferrocene$
complex
--
cz-25~;
L _.e
co>
.#i$t;
in
_*rj&~y~ph~spg.,le
ultravio&et:light gave-the complex (7.25;
t&z&
of
pp&zJ=ce
L =.PPh,],
_A
similar replacement reaction was carried out with diphenylacetylene.- Treatment of the complex (7.25; L = PPh3) with = hydrochloric acid gave (7-C5H5)Ni(PPh3)C1 and (7'C5H5)&in(CO)2PPh3 in good yields 138 .
The crystal and molecular structure
7.26
7.25
7.24
-cyclopentadienyl)bis(triphenylphosphine)of carbonyl();) manganese benzate
(~-C51i5)itiCO(PPh3)2.C6H6,has been obtained
from three dimensional X-ray data.
The compound has space
group 21 with unit cell dimensi-ons a = Ye83, C = 11.36 8; o(= 69.44O,p=
66.48,$=
67.57';
b-= 14.79, Z = 2.
The
P-&I-P bond angle was 104' and this large bond angle was considered to be a consequence of electrostatic repulsion between the two phosphorus atoms 139 . exchange in
The rate of proton
(tjI-C5H,-)>In(CO)(Ph2PCH2CH2PPh2) decreased in
acetic acid-trifluoroacetic acid mixtures as the acidity increased. stopped14'.
Mhen sulphuric acid was added the reaction almost The rate of-hydrogen-deuterium exchange in the
same molecule passed through a maximum as the acidity was occurred when the concentrations of the protonated and~nonprotonated forms were about equal 141 .
-increased.
Themaximum
The.cymantrene analogues (7.26;
H = CN, NCO, NCS, N3) under-
went addition reactions at the R group-wilth aIcohoIs,-amines le _ =+: _~~~>~~~ se-_Tertiary_add secondary carbinols of cyclopentadienylmanganese carbonyls (7.27) when treated with trifluoroacetic .acid give stable carbenium ions (7.28).
The carbenium ions
were identified by infrared spectroscopy and when one of the carbonyl groups was substituted by a phosphine ligand the stability of the carbeniua ion increased 143. o
The addition
OH
Q
o Q+R1
R2 CF3CO2Ii \
0
iin (co),so2
7.29
7.27
Ll, L2 = CO, PR
‘7.29
3
of excess trifluoroacetic acid to solutions of ( -cyclopenta7 dienyl)phosphinemanganese complexes (7-CTHS)i-InCOL2 and (7-C5Et5);VIn(C0)2L,where L = substituted phosphine and diphosphine ligands , gave rise to a &Yn-H proton NMR signal at 6 =.-4 to -6
ppm.
The stereochemistry of the protonated
forms was determined from the 1H-31P coupling patterns 144. The structure and bond lengths in the Tcyclopentadienyl compound (7.29) have been determined by X-ray methods;
Tht;-
manganese-cyclopentadienyl carbon distance was 2.09 a and appreciably shorter than in cymantrene compounds while the manganese-sulphur distance was shorter -than the normal covalent nond length by 0.3 8 145. Th& infrared and Rarnan spectra of (tj)-C4ilLLN)&ti(CO)3 and the infrared spectrum of (7-C4D4N)Mn(C0)3 were recorded_- _ References
p_ 288
238 and the vibrational frequencies were assigned.
The
frequencies of the C,+H$ ligand closely resembled those of the cyclopentadienyl ring in .(7-C5'~~)~~(CO>~...."~he replacement of a CX group by nitrogen had little effect on the,mechanical properties of the ring and the lowering of the local sy,mmetry of the ligand from _gV C to sS did not split the degenerate modes. However, the modes, active only in-the Raman spectrum of the cyclopentadienyl ring, for the pyrrolyl ligand also appeared in the infrared spectrum 146 . Nucleophiles were shown to combine with the cationic complex four different ways; rf7-C6H6)bti(CO)Jt In to the arene;
(a) by addition
when the complex was treated ivith (Et02C)CH-
it gave[~-C6H6CH(COzEt)z]?fn(CO)j;
(b) by attack at the metal
vxLth displacement of a carbonyl liganci; treaEaent
of the
complex with triphenylphosphine gavl[~-C6H6Mri(C0)2PPh~]*; (c) by attack at the metal with liberation of arene;
treatment
of the complex with methyl cyanide gave ~4n(CO)S(MeCI~)~]+; (d) by addition to the carbon atom of a carbonyl group; treatment of the complex with methanol gave (7-C6i56)Xn(CO)2COz;e147. 8. (Acyclic-+diene)Fe(CO)S
and (r?-trinethylenemethane)Fe(CO)5
complexes YlhenN-pyrone was heated with diirone.nnea carbonyl the tricarbonyliron complex (8.1) was obtained.
The ester group
in this complex zas highly reactive and underwent cleavage with methoxide to .@va the ally1 anion (ij.2).
Treatment
of this anion with acetic anhydride gave the ester (8.3)
and
treatr?lent yiith lithium aluminium hydride gave the aldehyde(e.h)14"..
The reaction of I\ieCH=C~CIi=CHCB(Ie)lUH2 (R = ii,Xe)
/c =n’
239
0
,.---‘,
0
0
t
rr
Fe
(co)3
AC
0
OCH3
Fe
S-2
8.3
with pentacarbonyliron gave the tricarbonyliron complex Alternative routes to this complex were also presented14'.
(8.5).
The reaction of Fe2(CO)v with the olefin FcCH=CHCH(OH)Me (Fc = ferrocenyl) in the presence of copper (II) sulphate gave (rj+FcCH=CHCH=Cii2)Fe(CO)3. In a similar manner FcCMe(OH)CH=CE2 gave (7-H2C=CFcCH=CH2>Fe(CO)3.
The dehydration
/7== \ 0
H
Fe
(CO)
3
8.4
6.5
3.6
of E-PC d CH=CXCH(OH)Me with copper (II) sulphate gave
64
E-FC6H4CE=CHCH=CH2 which when treated with Fe#C0)12 the complex (~-~-FC6H~CH=CKCH=CH2)Fe(C0)3150.
forned
Then:-ally1
lactan (8.6) when heated in methanol gave the iron-tricarbonyl complex (8.7)15". Aumann has obtained the vinylcyclopropane complex of iron
(8.8) from the parent hydrocarbon on irradiation-with iron References p_ 288
When the cyclopropane (8.8)
pentacarbonyl.
was heated in
benzene-it gave a mixture of the (ydieneliron compounds (8.9 &ntzaris
and 8.1C)!52.
and Weissberger have investigated
/\ +‘T,
Fe
(co)q
.
Fe
(CO) 3 8.8
8.9
..
8.10
the mechanism by ;V'hichcyclopentanones are formed through coupling
of olefins to carbon monoxide on irradiation with
iron pentacarbonyl.
Photolytically generated iron
tetracarbonyl first formed a (tj -olefin)iron tetracarbonyl complex which was converted to a bis(7-olefinjiron tricarbonyl complex through the intermediate (q-olefinjiron tricarbonyl. Cyclization to a metallocycle followed by migratory insertion of carbon monoxide led to the product 153 . The structures of two diene-iron tricarbonyls (8.11 and 3.12) having substituents in the ~JI-Iand anti positlons were determined by X-ray diffraction. -
as models for the parent
These_ compounds zere used
compound (q-butadienelircn tricarbonyl _ _
_-
. -.
241
and on the basis of their structures, the-structure (8.13) for the-butadiene molecule bonded to Fe(CO)3 (CSsymmetry) was proposed154.
(7-Pentadienyl)iron tricarbonyl cations may
a = b = c = o(=
3.12
8.11
1.404 B 1.415 1.08 119.8'
-p = 117" II = llYO s= 1180
have the structures (8.14, 8.15 or 8.161, the diene (8.14) and trimethylenemethane (8.15) structures are consistent with the K&N rule with an U-electron
configuration at iron.
However, the ally1 structure (8.16) with a 16-electron configuration at iron is consistent with the Dewar-ChattDuncanson theory of bonding in transition metal'7Gcomplexes. Structure (8.16) permits free rotation &bout the C,-C3 bond while this is not permitted by structures (8.14 and 8.15). Evidence for free rotation has been obtained by Bonazza and Lillya on treatment of the (7-butadiene)iron complex (3.17) The low-temperature with FSO !A in sulphur dioxide. 3 spectrum of the cation formed from the complex (8.17) -ctas not wholly consistent with a (t7-aliyljiron cation 155 .
Fe+ NOI
8.14 References
p_ 288
a.15
8.16
Pe (CO)
a-17
3
.
_
. Kruczynski.and Takats have investigated the fluxional behaviour
of-several (q-dienejiron tricarbonyl compounds-b-y variable .temperature '% RXR spectroscopy. A lox-temperature limiting spectrum was obtained in each case with a 2 : 1 ratio of basal ; apical carbonyl groups.
A mechanism (8.18+8.19=+
8.20) was suggested~for the basal-apical exchange157. .. 1
, CO1
-
7
CO2
I
1
2*/FeY
co3
,,,~
I
e
+
+3 co-’
3.19
8 .I_8
iron complexes. (8.21;
The
,/w\ 0:.
A1
8.20
R = H and Me) were characterized
by protolytic reactions, mass spectrometry and 'H and 31P Mk? spectroscopic studies 1%. R
3.21
Brookhart and Harris have reinterpreted earlier results on the proto&tion.of a general=toGchange
polyolefinic metal complexes 'interms of in metal ligand bonding.
This has
been exe:aplifi.edfor (7-butadiene)iron tricarbony2 (8,221
_. _
,
which gives the-3-allyl G-iron-cation
(8;23) that undergoeses
intramolecular proton scrambling by equrlibration with-a-~ small proportion of the q-ally1 cation (8.24)1=.
nI
--'
+
Fe
'Fe
(CO13
(co)3
8.22
Iron
5.23
8.24
tetracarbonyl and iron tricarbonyl complexes (8.25) of a$-unsaturated
carbonyl conpounds have been treated with
acetylium tetrafluoroborate to give yellow, crystalline air-labile salts which may be formulated as either ally1 (8.26) or enone (8.27) complexes.
These salts are decomposed
easily by nucleophiles such as methanol and water to give the original enone complexes (8.2~)~~'.
8.25
Whitesides and Slaven
::.26
have investigated complex formation between the a-
8.27
and
trans-isomers of Feist*s ester (8.28) and diironnonacarbonyl. -. The first formed products are aand trans-(7-olefin)iron tetracarbonyl compounds (8.29) yfhich then undergo ring opening and a series of stereospecific reactions to give_eventually References p_ 288
.- anti- and syn;&dieneIiron 8.31)
respectively.
*isomer (8.29)
tricarbonvL corn&.e~
(,S,~Qand
.The photochemical reactions of the cis
parallel the thermal reactions whLLe the trans gave a q-ally1 complex 161 .
isomer (8.29)
.
_
The attack of several open-chain pentadienyltricarbonyliron cations (8.32)
on 1,3_dimethoxybenzene has been studied
kinetically.
The trans-pentadienyltricarbonyliron Me0 C
i-ieO,C Fe2(CO)
_9
cation
2\
L
i b
Ple02C
-+
Ie02C
8.28
Gl,
8.29
Fe
m3 8.31
ite02C
1~ -b
\
;-ie02 C \
(E,, 3.30
(8.33) was postulated as the reaction intermediate and only one product (8.34)
was isolated 162 .
iron tetrafluoroborate (8.35)
Pentadienyltricarbonyl-
was treated with a series of
246
either one exomethylene group exchanged:'lithone ring methylene or.that.the hydrogen atoms were reversibly exchanged betvieen 165. The the ring carbon atoms and the exocyclic carbons c~
E2-
H
H2
-*CDT D2c Fe (co)g
2
W C"i2
3 Cj$ '2
IZ2gCIi2 Fe OCo)j
G),
8.45
2.44
3.43
monomer (y-2,4-hexadiene -l-y1 acrylate)tricarbonyliron
(8.46)
was prepared from pentacarbonyliron by the routes shown (Scheme 8.1).
The monomer (8.46)
was honopolynerixed and
copolymerized with acrylonitrile, vinylacetate, styrene and methyl acrylate in the presence of azobisisobutyronitrile as the initiator.
The polymers were characterized by infrared,
gel permeation chromatography, viscosity and differential scanning calorimetry studies.
When the polymers were
166. decomposed_thermally in air iron (111) oxide was formed The crystal and molecular structure of a?-trimethylenemethane complex of iron has been determined by X-ray methods. The complex was formed from diironnonacarbonyl -2(bromomethyl)naphthalene167.
and l-bromo-
The gas-phase infrared and
Raman spectra of trimethylenemethaneiron tricarbonyl were recorded and interpreted 168 . The butatriene derivatives
-
_
247
8.46
Scheme
(8.&a;
Rl = Ph;
8.1
R2 = t-Bu, e41eC6H4, p-MeOC6H4, Ph,
o(-naphthyl; R3 = Ph, t-Bu, z-MeC6H4, &-MeOC6H4; t-Bu, Ph, E-NeC6X4, &4eOC6Hk,
R+ =
o(-naphthyl) gave a series
of complexes with Fe3(CO),16g. R1 \
I<3
C=C&=C
/ ,22 9.
/
8.46a
>4
(q-C,,H,,)?e(CO)
3
9.1
The carboxylic a&d References
p. 288
9.2
9.3
(9.2) has been synthesized conveniently
248
-
by irradiation of the pyrone (g.l),.addition of an excess of iron pentacarbonyl to the photoproduct-and further irradiation. The product (9.2) was obtained in 21% yield after saponification and the intermediate ester (9.3) was also isolated The isomeric tetrahalocycloas a light sensitive oil 170 . Br
Br 9.6
9.4
butanes (9.4;
R1 = R2 = H or He) were treated with Fe2(CO)g
to give the cyclobutadiene complex (9.5;
R1 = R2 = C02ile).
This complex was converted to the optica$ly pure Complexes and R' = (9;s; R1 = Et, R 2 = tie; R1 = C02xe, R2 = COIule C02S, R2 = COMe)171.
Methoxymethyl-3, 4-carbonyldioxycyclo-
F 0
d
9.3
0”: 0
0
9.9
butene was treatetiwith disodium tetracarbonylferrate to give (q-methoXymethylcyclobutadiene)iron tricarbonyl which was converted to the bromornethyl derivative (9.6) acid;
by hydrobromic
The treatment of this derivative (g-6) with potassium
249
(coLj 9.10
9.11
alkoxides gave the complexes (go7;
n = 1,
a.
Successive
photolysis and Ce (IV) oxidation of the complexes (9.7; n = 1, 2
gave 5-methylisochroman (9.8) and 4-methylphthalan
(9.9) respectively172. By the use of reasonable approximations a valence force field has been calculated for tricarbonyl(T-cyclobutadiene)iron using s4x symmetry for the C4H,+ group and + RFe(CO)g moiety.
for the
The results obtained reproduced the observed
vibrational frequencies very closely and were consistent with those known for related systems173. complexes (9.10;
Irradiation of the
R = But or Ph) in hexane afforded the
binucleer derivatives (9.11;
R = But or Ph), these complexes
were converted back to the starting materials by treatment with carbon monoxide. (9.11;
The crystal structure of the compound
R = But) was determined by X-ray diffraction.
The.
two iron atoms were bridged by three carbonyl groups and the cyclobutadiene ring was essentially square planar.
The
Fe-Fe bond was extremely short, 2,177 8, and it was thought that a triple bond existed between the t%ioiron atoms.
This
gave the iron atoms eighteen electron configurations and it also accounted for the diamagnetic behaviour of the complex 174 o The structure of (tj3-cyclobut&diene)iron.tricarbonyf has been studied by microwave spectroscopy and it has been References
p. 288
J ’
confirmed spectra obtained
as
symmetric-top
of-(7-cyclobutadiene)iron for the liquid
and 13C NMEtspectroscopy between:the
phenyl
tricarbonyl
group
‘Tne
tri&.rhonyl
and solid
frequencies assigned176 .
175 _
molecule
phases
IR
and
Raman
have been
and the vibrational
Brune and Horlbekk have used 'H to investigate
substituent
and the
in the complexes
electronic
interactions
(?J-cyclobutadiene)irod
(9.12;
R = H, F,;Cl, Br).
group donates eILectrons,by conjugation The:(t)-G4H3)Fe(CO)3 and accepts electrons molecule177,
through
The 100 i%&
the S.&PAZLskeleton
of i&e
'H M4R spectra of chloro-, bromo-
and methyl-cyclobutadieneiron
tricarbonyl
were recorded
and
analyzed178.
The ca.rbaxy3.i~ acid addition
(9.13)
has
of trichloroacetonitrile
tricarbonyl-and r-k&rw~~&~~
alkaline_ hydrolysis
imtanvadfate.
been prepared by Hoes&z-
to (v-cyclobutadiene)iron of>the
-The acetic
resulting-.tri-
acZd
derL.ative
__
<4,1%>~
was obtained-by displacement of chloride from C?&hXoromethylcyclobu~adienefriron tricas%onyl: uriQ~ cyanide and hydrolysis of the acetonitrile derivative. aGa&. as
cgmYL_3cizK%?8.14)
5.C33
Mt?idS--It
5.56
end WSS
CtSnC~CC&?~
The PK, values for-the two
in Jx?$
wer-e %zeasur&
respeciXvely. t&St:
.
ef&zal
aqueGzzs
Gn the %asis of t&es6 measure-
CrT-cycl~~~tra~~ene)~rU~
k~~CZII%KXS~~
is an erectron releasing group by resonance and a weak electron withdrawing group hy induction 179, q-~c~tyzrgc~o~~tadieRa}iroR
pin‘acol-reduction of
triCEtX%ORy~
~gZk+S
t&3
#-C-ii&
(9.15)
which'was dehydrated to-the diene (9.16) and underwent pinacol rearrangement to the ketone (9.17). -- Reduction of the same acetyl derivative
with
diborane_ gave
(v-ethylcyclobutadiene)-
iron tricarbonyl and acetylation of this product gave a 9 : 11 mixture of the 2- and 3-acetyl derivatives.
Treatment-of
(v-acetylcyclobutadiene)iron tricarbonyl with base led to the isomer-it dypnones ~9.~@0.
OH
Grey has descr5bed the
OH
5+--T 0
0
fe
Fe
(co>3
(COlg
9.16
9.17
9.18
252
.
decomposition of an optically active (7-cyclobutadiene)iron tricarbonyl derivative with ceric ammonium nitrate in the presence of dienophiles to give totally race&-products, These results supp0rted.a mechanism of decomposition where 'free cyclobutadiene was an intermediate 181 . The iron carbonyl cation (9.19) has been formed by hydride abstraction from a benzocyclobutenyl precursor.
The structure
(9.19a) is preferred to the alternative (9.19b) on chemical grounds
and
degradation through
the
it
may
be
of
(7 -cyclobutadiene)iron
sequence
an
intermediate
the
o-dative
tricarbonyl
182 .
(9.20.+_3.24)
@+
in
complexes
Irradiation of the
-g+
F&(C0)2 I .-w\ \ .‘1
Q V.;Vb
9.1?a
n+
n+
7 G
>
la’
01 '7
Fe
Fe
(CWg 9.20
9.22 nc -
7
9.24
1
Fe
(solv)
B-1 3.23
253
benzocyclobutadiene complex (g-2.5)with iron pentacarbonyl gave the diiron complex (g-26) as the major product together with minor amounts of two isomeric diiron complexes (9.27 and 9.28)
and two triiron complexes (9;29 and 9.30).
complexes (9.27 and 9.28)
The
were formed by an unusual ring-
-opening of the cyclobutadiene group and gave the triiron complexes (9.29 and 9.30) respectively by coordination of a third iron tricarbonyl residue 183 _
Fe(CO> 3 \
(CO)3Fe-qT5;3
v7cCo)3
+ q&o)3
+ 3 g.23
Fe w3
9.29
9.30
Fe w3
(3-Cyclobutadiene)iron tricarbonyl was stirred with nitrosoniurs hexafluorophosphate in acetonitrile to give the
PF
9.33
6
air-st~b~e__cryst&ine addition-of
trialkyl
butadiene. cation When
complex or triaryl
(9.31)
the hydrocarbon
complex
by heating
Complexes.
under
complex
with diiron
then the complex _
to the 7-cyclo-
diiron
nonacarbonyl
of carbon
monoxide
in to
An iron carbonyl
control
nonacarbonyl
cp. \- +
gave
from the reaction
nonacarbonyl.
of homosemibullvalene
10.5 and 10.6)~~~.
~- 10.3
(9.32).
(i) Formation
(10,1)186.
(10.2) was obtained
under kinetic
I
complex
10.2
[4.1.0]heptane
diiron
with
an atmosphere
10.1
reaction
phenyl
in acetone
dimer was cleaved
the pentalene
derivative
to the ?-cyclol
(9.33)185.
methylcyclohexane give
phosphines
(H) were
10. _(Cvclic-n-diene)Fe(CO)z
Pentalene
Eucleophilic
gave the .q-cyclobutenyl
groups
(9.32) was converted butadiene
(9.31)&*4_
The reaction with
Fe(CO)5
The light-induced
(10.3) with
the iron
benzo[&]
hy
pentacarbonyliron
carbonyl
of iron
of bicycle
compounds
pentackbonyl
thiophen-l,l-dioxide
I CD
(10.4, or gave
\ -Fe(COj4 .
10.4
.
10.6
10.5
the two co:aplexes (10.7 2nd X.8).
- The structure of complex
(10.8) was confirned by X-ray crystallography188.
10.8
10.7 iron carbonyl complex (10,9;
The diene
10.9
-
R' = alkyl, R2 = H) was formed by
treatment of the appropriate silacyclopcntadiene aith diiron nonaThe same complex (10.9; R1 = alkyl, R2 = ii) czrbonyl 189. y{as
ureParod-independently by a second group using the same *
reactant&.
The corresponding tetraphenyl complex (lO.g;* R" = _ .
alkyl, R2 = Ph) was also prepared from the tetraphenylsilacyclopentadiene 2nd iron pentacarbonyl. R1 =
Xe,
The complex (10.9;
R2 = Ph) was obtained from_l,l-dimethyl-2, 5-diphenyl-
silacyclopentadiene
by treatment with bromine to form 2 .
mixture of the ,?,3- and Z,5-dibromo adducts which were then .= heated with diiron nonacarbonyllgo. Photolysis of pentacarbonylfron and the 2-vinyloxiranes (10.10;
33 = H,
ReferenceSp.288
Me;
X i “H2,
_
CH2CH2> gave the lactones (10.11).
iTlien the
la&one
(lO.11;
H = k, X = CH2CH2) was heated- in
benzene the complex (10.12) was formed w_
Treatment of the
cyclohexene (10.13), prepared from l(diethylamino)butadiene and Cki2=CkJR, with Fe3(CO)p2 gave the Irontricarbonyl complex (10.14; R = CHO,
COble)192.
The cyclohexa-2, 4-dLene c~p~ex
ILo,
10-14
(10,Is)
10.15
was prepared by heating the correspond%ng cyclohexa-2,5-diene with iron pentacarbonyl.
The rearrangement may occur by a
l,s-hydride stift frozna methyl. grozp to the exomewiglene grou_n in &&ch
the iron carbonyl group participates 193 -
The
stereochemistry of the interaction between diiroa nonacarbonyl and cisoid or transoid divinylcyclopropyl ligands has been examSned by ~zsing the spir0norcaradiene (10.16) as the ligand since
this
ligand contains both cisoid and transoid systems
in the sazzemolecu1e*
S==Id conditions (room temperature,
257
10.18
10.16
Details were given for the preparation of tricarbonyl(v-2,4-cycfohexadienone)iron and tricarbonyl(t?-2-methoxy-1,3-cyclotexadienylium)iron hexafluorophosphate from anisole l%,l%_ Their conversion to tricarbonyl(l-ethoxycarbonylmethyl-l-hydroxy-2,4-cyclohexadienejiron
(10.19) and tricarbonyl
~?-(2-hydroxy-4,4-dimethyl-6-oxo-l-cyc~ohexen-l-yl)-2-methoxy-l,+cyclohexadiene]iron
X0
cii2c025t
0 \’
I
I
(10-20) respectively was described1g7S1g8.
258
Dodman and Tatlow have described the preparation of some (7-polyfluoro-1,3-cycloheptadiene)iron (10.22;
tricarbonyl complexes
X = H, F) from tr~Grondodecazarbony1 and the ligand
in sealed tubes at 130°.
Pyrolysis of the complexes at 440° C
under nitrogen gave polyfluorobenzenes, presumably by loss of iron tricarbonyl and fluorine to form polyfluorocycloheptatrienes Yfang and Paul have prepared an land then ring contraction 200 . iron tricarbonyl complex of barbaralone in which.the hydrocarbon
may be bound as a uhomobutadiene" ligand (10.23)-
This
proposal is-supported by X-ray structure analysis and molecular spectra201-
Details have been given for the
synthesis of bis(v-1,3,5,7-cyclooctatetraene)iron tris(2,&pentanedionato)iron,
(0) from
1,3,5,7-cyclooctatetraene and
triethylaluminium202, The cis4 -cyclononatetraene conrjlex (10.24) has been _ . prepared from a-bicyclo[6.1.0]
nonatriene either thermally
v:ith diiron nonacarbonyl or photochemically vrith iron pentacarbonyl.
Three other (7-CgHLo)iron carbonyl complexes
were isolated and characterized from the same reactfons. W-iile the parent hydrocarbon ligand underwent rapid electrocyclic ring closure to dihydroindene at 23O (t+
= 50 JKL~,
259
dF*=
23 kcal mol'l); the complex is stable at room temperature
for several days hut underwent first-order isomerixation to .
the dihydroindene complex (10.25) at 101' (k = 2.4 x 10m4 set -l, BFf= 28.4
kcal mol -5 .
Protonation of the tetraene
compound (10.24) occurred at C6 in FSO H at -120' to give the 3
dienyl cation (10.26)203.
/\ \ 0
The reaction of 1,7-cyclododecadiyne
H2
+
1
H2
'/ I
Fe
G,,
(co)3
10.24
10.25
10.26
(10.27) with Fe(C0)3 unexpectedly gave the ferroie (10.28) rather than the ferrole (10.29)204.
It was suggested that-
the formation of (10.28) proceeded through the (r;)-cyclobutadiene)iron tricarbonyl complex (10.30) from (10.27) and Fe(C0)5, and further reaction of the complex (10.30) with Fe(C0)5 to give the ferrole (10.28).
This suggestion was supported'by
the combination of the iron tricarbonyl derivative (10.31) with excess Fe3(CO>12 to afford a mixture of the sym- and unsym-benzoferroles (10.32) and (10.33) respectively205,
10.27 References p. 288
10.28
-260
Irradiation
iron cations
of (v-dienyl)tricarbonyl
n = l-3, R = ii, ONe) in the presence l,+diene
gave
R1 = If, OXe; of these reagents
10.33
10;32
3_0*31
the cations
(10.35;
(10.34;
of the appropriate m = 0, 2, 3;
n = 1-3;
Rz = H, Xe) in good yields.
The reactivity
cations
towards nucleophilic and electrophilic 206 In an investigation of the photo. was examined
Fe
(SO)
3 10.35
10.34 -reactions 3-hexyne chloride
of cyclopropylacetylenes was irradiated
with
with iron
iron pentacarbonyl
carbonyl, in rnethylene
to form the benzoquinone adduct (10.36) in addition 207 . The irradiation of Fe(CO)5 to the free benzoquinone
261
Et
Et
0
i30
_I_ I
Et
(Ei,
I
zt
Fe 3
(CO)
10.36
3
l-O.38
with cycloocta-1,5-diene and cycloocta-1,3-diene gave the corresponding (y-diene)irontricarbonyi complexes (10.37 and 10,38).
On reaction
-ion abstraction
of complex
occurred
to
complex ~'I-C&1)Fe(CO)3]+ The direct
reaction
(10.38)
give
the
with Ph3CBF4 hydride-
cyclooctadienylium
208.
of pentaborane
(9) with
the reaction of tetraborane (10) with Fe2(C0)9
ferraborane B4H8Fe(C0)3 (10.39).
Fe(CO)5
or
gave the stable
Spectroscopic evidence showed
that the i?e(CO)g group had replaced
the .apical BH group in
B5k19and that tke compound had structural and bonding affinities y/ith (7-C4H4)Fe(CO)3
and Fe5(C0)15C
2og.
0
0
a aD 0
(ii) S;ectrosco:>ic The structure
References
p_ 288
II Fe 0
c 3
and Physico-chenical
of the tricarbonyliron
10.39
%udies coiplex
(10-40)
262
The Fe(C0)
was determined from X-ray data.
3.
moiety was t
bound to-the diene portion of the cyclohexadiene ring and this six-membered ring was e-fused
to a four-membered ring, ?zhich
in turn was cis-fused to a second four *membered ring. . Both 210. The molecular four membered rings were essentially planar structure of the (q-diene)iron compcund (10.41) has been The ligand determined by single-crystal X-ray analysis. The crystal and molecular adopts the boat conformation 211 _ ‘.r(i H-3
1e f
OTC)= 0
7 G,, .
Fe
WO13 10.40
10.41
.
10.42
structure of 3,35'-bi8(7-bicyclo[4.2.0]octa-2,4-diene-tricarbonyl-ironj, analysis.
C(~-CgHg)Fe(C0)~2
was determined by X-ray
Phe structure consi8ted of two bicyclo[4.2.0]octa-
2,4-diene-tricarbonyliron moieties related by an inversion centre212.
Struchkov iias reported bond lengths based on
Z-ray neasurements for the iron complex(10.42)213. has
determined
tke
bond
length8
and
Struchkov
interatomic‘distances in
the cyclopentadiene complex (10.43) by K-ray method8213. The structure of tto iron complex (10.441,
containin&, two r different valence-tautoueric forms of thev-C8Hlo~ligand,
has been determined by x-ray crystallography.
90nd length
alternation in the parts of the ligand8 bonded to the iron atom was not observed and these parts of the ligands were planar214.-
The crystal and molecular structure of a tri-
263. carbonyliron derivative of barbarlone (10.45) has been determined by X-ray cry.stallographSi. The compound crystallized
/-4 0
7e(CO)3
L -. --2s
10.43
10.44
10.45
from pentane at -5' in the triclinic system with unit cell dimensions a = 7.48, b = 11.91, c = 6.61 8,oC= 94.55', /3= 110.17', y= 92.38', 2 = 2 space group l??carbonyl groups were mutually cis.
The three
The ally1 group was
trans to two of the:aand the Fe-C sigma bond was trans to the third carbonyl group 215 . The 57 Fe Aoessbauer spectra obtained on glassy n-butylbenzene matrices of the tricarbonylferroleiron tricarbonyl derivatives (10.46, 10.47 and 10.48) were analysed. The two nonequivaLent ircn atoms were resolved and the doublet with a quadrupole splitting in the range ~22-1.26
mm/set
was assigned to the iron atom of the iron tricarbonyl group bonded to all-four carbon atoms of the ferrole ring,
The
doublet at-a less positive isomer shift with a quadrupole splitting in the range 6.9$/1.02 mm/set was assigned to the iron aton-in the ferrole ring 216 _ The electron-impact induced fragmentation of thirty derivatives of the styrene complex (10.49) has been studied References p. 288
_ m-m
g--L
mym
f
.(Cqn
$
-A
(S5
Fe (CO) 3
\
2)n
Fe(Co)3 \\ Fe(CO)3
Fe
("X2)m
(co)3
*.
-10.46 R = Xe, Et, Ph
by -mass spectrometry.
10.47 fi = 4, 5, 6 Zl1= 4, 5, 6
10.48
In each case the complex underwent
stepwise loss of carbon monoxide groups followed by loss of iron atoms as in the following scheme (Scheme 11.1)
~~-vinylstyrene)l?e2(C0)6]'_
kv-vinylstyrene)Fez]' .
[Q-vinylstyrene]+
C--
t(T-vinylstyrene)]Fe+ 3
Fragmentation of the organic ligand was sensitive to the nature and position of the substituent, at least four modes of breakdown were observed 217 . Infrared and Raman spectra of (~-N-methylmaleimide)iron tetrac-arbonyl (solid, solution) and of N-methylmaleimide (solid, solution , gas) were recorded.
An assignment of the
normal modes of both molecules was made and compared with the data for (q-maleic anhydride)iron tetracarbonyl.
The C=C
stretching vibration in the complex occurred at 1370 cm" co.mparedaith 1585 cm-1 in the free ligand218.
as
Andrews and
Davidson-have also investigated the vibrational spectrum of (q-maleic anhydride)iron tetracarbonyl.
On the basis of
265
solid-phase infrared and Raman spectra,' together
with
some
solution data for the infrared, a complete-vibrational assignment was made for the modes of maleic anhydride in the complex. Shifts in 3(C=C) and 6(Cii) were consistent with a strong interaction with the metal, but relatively little coupling between the modes21g.
These.results agreed in all essential details with those presented by Lokshin and co-workers 218 .
10. (iii) General Chemistrs Treatment of the (7-cyclohexadienyl)iron tricarbonyl cation with sodium alkoxide (NaOR) gave the iron containing cyclohexadiene ethers (10.50; in good yield,
R = Pa, @GeOC6H,+, 3,_5-;'re2C6H3)
Treatment of the same cation with (v-5-hydroxy-
-1,3-cyclohexaciienyl)iron tricarbonyl gave the ether (10.5~1)~~~.
Fe
Fe
GO)3
(CO13 10.51
Irradiation of (v-g-quinodimethane)tricarbonyliron in the presence of pentacarbonyliron'gave the t'hree isomeric complexes
.-,
--
_
_:
(10.52,
X.&and
10.54)zz1.
has been-shown aromatics. benzene
The dienyl
to act as an electrophile
Thus
l,+dimethoxybenzene
gave the diene-substituted
following
reaction
(Scheme
/--.+ (.I_: ‘0.
cation towards
benzenoid
and 1,5,5-trimethoxy-
Rroducts
10.2).
(10.55)
Rate
(10.56)
constants
in the for the
1
BF4-
+’
_*s
I I
10.55
Fe
(co>3 Scheme
reactions
were measured
for the reaction
10.2
and compared
of the cation
to give the order
kth
(10.55)
the rate
with some
heterocycles
nyrrole?indole>
of reactivity:
constants
furan)
1 ,3,5-trFmethoxybenzene>l,j-dimethoxybenzene)thiophen. Preliminary
experiments
;'rasalso an active
indicated
electrophile
that
[(v-C71$.)Cr(CO)3]+
towards
heterocycles
such as
-indole222. The pentadienyl the diene
complexes
cation (10.57;
vfith tri~A~enylmethy1 cation
(10.<9;
these
cations
the diene
complex
(10.60)
Ii = Xe) .
enamines,
li'thiums have been studied.
formed
from
by treatment
The methylpentadienyl
formed under
(10.57;
(10.59) with
R = a) was
R = I-I and 10.53)
fluoroborate.
R = fie) was
fro.5 the diene.complex
(10.59;
the same conditions The reactions
alkoxides
The cation
on treatment
..
of
and alkyl-
(10.59;
R = II> gave
with alkoxide
ion andd
Q \I / I Fe
OS3
with the enamine (10.61) it gave the complex (10.62) after hydrolysis223.
Experimental evidence has been offered to
support the hypothesis that (v-cyclobutenejmetal complexes can undergo a facile, disrotatory, concerted rLng openin& of the complexes, four-membered ring to give ( -butadiene)metal 7 The iron-olefin complex (10.63) has been heated in hexane to form the iron-diene complex (10.65) presulqably through the intermediate (10.64). to solvent
The rate of.conversion is insensitive
polarity.and the reaction is inhibited by carbon
monoxide and added olefins 224.
~.
--:. The reaction of (7-bicyclo[3.1.O~bctadienyl)Fe(CO)3~ --CXOi66) vfifh pyridine gave the cyclooctatriene complex (10.67) -_ .. which-was . transformed into the corresponding cyclooctatetraene .. complex (10.68).
The addition of iodide ion to the complex
(10.66) caused the cyclopropane ring to open to give (3,&,5-~-octatrienyl)Fe(CO)-J225.
The fluxional cation
+
I
Fe (CC) 3
Fe (co)j
lo.66
i-
10.67
inJ+
10.63 (10.69) was prepared by acid treatment (HBF,+-Ac20) of the alcohol (10.70) or its isomer (10.71). ,
Treatment of the
cation (10.65) --ith triethylamine gave the dimer (10.73) via the unstable (7-heptafulvene)iron tricarbonyl complex (10.72). The structure of the dimer (10.73) was confirmed by an X-ray investigation 226 .
+ 1
i69
w 1’
\I
1
\.I/-
I
I
Fe
Fe
(co)3
10.72
GOI
IO.73 of solutions of (r)-cycloheptatriene)iron
Irradiation
tricarbonyl and acetylene dicarboxylic ester in tetrahydrofuran gave the complex (10.74).
6fi]addition had taken place and
demonstrated that [k+ X-ray data indicated to the triene bonded.
that the acetylene
on the same
This
The isolation of this compound
suggested
moiety
had added
face to which the iron atom that at some
xws
point in the reaction
the acetylene was bonded to the iron atom.
Irradiation of the
complex (10.75) with acetylene carboxylic ester gave the complex (10.761~2~.
The reduction-of tricarbonyl(l-_5-7-
-cycloheptadienylium)iron with sodium tetrahydroborate resulted
$-Jy2- PO) 2-e
(co)3
CO
lo,742
.2e
Fe
GOI
10.75
in nucleophilic attack at both the l- and 2-positions to generate
a mi.x*Jre of tricarbonyl(7 -cyclohepta-1,3-diene)iron
(10.77)and tricarbonyl(3-5-7,l-Ckyclo-heptenyl)iron Tricarbonyl(l-T-7-cyclohexadienylium)iron
(10.78).
and its dicarbonyl-
(triphenylphosphine) analogue both gave the corresponding References p. 288
.-
10.73
10.77
10.79
cyclohexa-1,3-diene product (10.79; L = CO and P?h3> when 228 . treated withsodi&tetrahydroborate The mechanism of the thermal isomerization
_
of the octa-
tiene complex (10.80) to the more stable complex (10.82) has been investigated.
b-V Tne reaction foll.owed first-order
kinetics with a free energy of activation of 31.3 kcal mol'I. Both kinetic and analytical evidence indicated that the cycloocta&iene
complex (10.81) was the intermediate in
the rearrangement22g.
Thermolysis of (7-a-bicyclo&,l.O]
p-0
I
Ye
Fe
(CO> 3
(co)3 10.81
10.s2
nonatrieneldiiron hexacarbonyl (10.83) involved rearrangement of the organic ligand to give four iron (10.84, 10.85, 10.86 and 10.87)230.
carbonyl complexes
i'ihenthe cyclooctatetraene
R3 = i!, 3' CPh3) tiere heated-in a sealed tube in octane they rearranged complexes (10.d8;
CPh R1 = Ii,SiNe3, R2 = -'-,
to give the isomeric bicycle. [4.2-O] 2,4,7-octatriene compounds iXo.sg;- 4
= SiMe _.3, CPh3, X2 i H,Si>Ie3)~
.
The crystal and
.
271
m ‘iFXFe c-
-I-
:
I
\
/
\
&
1
(CO13
(COj3
molecular structure of the complex (lo-S91
•!-
/b I I J,
10.85
I/
A
Fe-Fe
10.86
(c0),(c0~, was determined
by X-ray analysis231.
via
The synthesis of bicycle [6,2;0]decapentaene derivatives 232 . the tricarbonyliron complexes has been reported
Kinetic studies were carried out on the reactions of tricarbonyl(7-cycloocta-1,3-diene~.-,tricarbonyl(7-cyclohexa-l,3-diene)-, and tricarbonyl(7-cyclohepta-1,3,5-triene)-iron couqlexes with triphenylphosphine.
In the presence of excess
triPhenylphosphine tricarbonyl(7-cycloocta-1,3-diene_)iron underwent a second-order process to form trans-[Fe(CO)3(PPh3)2].
In contrast, tricarbonyl(i')-cyclohepta-l,+diene)iron and ~_ tricarEonyl(q-cyclohexa-1,3-dienejiron e-
.<~~
did not combine with
The Gtter complex underwent a PPh, under these conditions. /CO-dissociative reaction at high terfiperatureswith retention of the olefin.
-cyclohepta-1,3,5-triene)iron Tricarbonyl(rjr
was similarly-unreactive but it underwent reaction with
Pph
3
at l.Y+°Cvia first and second order processes 233.
11. (?-C5H,)Fe(r)-C~E6)f " , Ferrocene, in the presence of aluminium chloride and aluminium, attacked a number of polyaromatic molecules to give derivatives of the (q-benzene)(q-cyclopentadienyl)iron cation. Biphenyl, diphenylmethane, fluorene, g,lO-dihydroanthracene, g-terphenyl, anthracene, phenantzhrene, pyrene, chrysene and other aromatics each bonded two (y-cyclopentadienyljiron groups to give dications which were isolated as the yellow hexa-fluorophosphate salts.
The structures of the salts were
determined by 13 C Ni-II? spectroscopy and those of 9,10-dihydroanthracene
for
the complexes
(11.11, terphenyl (11.2) and
phenanthrene (11.3) are typical 234 _
Electron-rich aromatic
compounds behave as donors towards-bis(v-hexamethylbenzenejiron (II) hexafluorophosphate and give 1 : 1 molecular complexes,
273 Benzene,.antbracene, anilines, hydroquinone, pyridine, furan and ferrocene have been used as donors,
In the last case
the-complex (11.4) appears to have four stacked rings 235.
The treatment of bis(rjl-nesitylene)iron(II) hexafluorophosphate (11.5) v.ith a series of nucleophiles (N) gave the mono adducts (11.6; N = CIT, CH2N02, CmleN02, CH2C02Bu t ). The reaction of (11.5) aith several oxygen and nitrogen nucleophiles (e.g. IJeOLi and H2HLi) gave the same product (11.7) which was thought to be formed by the initial attack of a base on anti-proton of (11.5) followed by carbanion addition to another ion (11.5) and finally fragnentation 236 .
(q-i3enzene) t
d’ P 0
_
d P
,.-4
‘
0
le
0
11.5
‘._H
Fe
D 0
11.6
Fe
PF,’
0
11.7
(7-cyclo?entadienyl)iron exhibited a reversible anodic References p. 288
0
polarographic wave at E3 = 1.23 V and an irreversible cathodic wave at E, =--2.19 V, both of these waves involved a single electron2% _ Bennett and Smith have prepared (7-arenejdi-p-chloro-ruthenium complexes (11.8) by dehycirogenation of the appropriate cyclohexadiene with-ruthenium (III) chloride in ethanol., .
.
These
complexes are cleaved Xith grcup V ligands to forn mononuclear complexes (11.9;
L = PH3, AsR3, pyridine) that are formally
analogous to benchrotrene.
The arene groups in the complexes
(11.9) say be exchanged on heating or irradiation in an aromatic solventz3'.
n
Giethylferrocene carboxylate
xas
treated with lo3RuCl 3 to give methylruthenocene carboxylate -103&39_ The IH spectra of ferrocene, ruthenocene and osnocene were obtained .
from monocrystal films and the Laser-Raman spectra were also obtained fro-msolid
samples.
was recorded for a solid film.
The IR spectrum of niclrelocene Fundamental symmetry forbidden
modes were observed for these solid state spectra and the fundamental vibrational modes were assignedz4'.
The
temperature dependence of the ghotoluminescence.of ruthenocene has been investigated by analysis of the luminescence decay
times in the temperature
range
4,2-77B-R,.
The energy
levels
of the lowest
excited states together with their decay character-. vfere obtained and were used to describe-the splitting
istics
of
a 3El(ddj
term into A
spin-orbital
coupling.
luminescence
spectrum
+ A 1 + El t E2 components
2
A J?ranck-Condon analysis
benzene
on polystyrene
beads
have different
that separation
occurs
of the cation with iodine,
(12.1),
the iodine
ligand
are reduced
rings
by 16'.
by 0.01 8.
have been
expected
oxidation
state
has been
coefficients
by X-ray
This shortening
of ruthenium
indicating than
structure
of ruthenocene
crystallography.
and tilted
back
from
bond distances
is less than would
of the increase from Ru
The three
rather
and molecular
The metal-carbon
in view
examined..
by the oxidation
are eclipsed
and
27; divinyl-
interaction
The crystal
has been determined
The cyclopentadiengl
with
distribution
formed
ruthenocene
crosslinked
by solute-gel
sieving 242 .
by molecular
13.
of ferrocene,
and s.:ollen in cyclohexane
metallocenes
of the
at 4.2O K was made 241 _.
The gel c!rromatography osmocene
by
in the formal
(II) to Ru(IV)243.
w-c,~H4)coo7-c~H) 3urther
been reported.
References
p_ 288
routes
to the q-cyclobutadiene
q-Cyclopentadienylcobalt
complex
dicarbonyl
(13.1) was
have
treated with bis(trimethylsilyl)acetylene
to give a binuclear
intermediate which formed the product (13.2) after reaction with a second molecule of-the acetylene.
Heating cobaltocene
with the-same acetylene also gave the complex (13.1). yields were obtained in
Q 0
i-ie3Si
Xe3Si
case 244 .
each
Low
The reaction between
Q 0
itosiHe3 0
xx
SiBe3
Ph
Co SiXe3
-YX Rl
0 R2 13.2
23.2
J-3.3
(7-CyClopentadienyl)dicarbonylcobalt and phenylethynyltrimethylsilane produced a number of organometallic products (13.2, R1 = Ph, Sine=., R2 = Ph, SiNe3; 13.3, RI, R3'= Ph, R2, R4 = SiNe R2 , Ii4 = Ph, Rl, R3 = SiHe R2, R3 = Ph, Rl, R4 = 3; 3' SiRe3) but no cyclotrinerization products were isolated. The structure of one of these products (13.2, Rl = Si& 3, R2 = Ph was determined by X-ray analysis.
The cyclopentadienyl rinb
was planar and had nornal Co-C and C-C distances.
The
cyclobutadicne ring was planar and the four C-C bond distances were equal.
The internal angles of the ring :fere not 90'
but the tivoangles at the carbon atoms bonded to phenyl rings were 88.1-O ar?d 88.4' iJl:ilethose bonded to silicon had values of 91.6~ :lnd g1,8°24so l,+Dilithiotetraphenylbutadiene
combined with
(7-C5H5)Co(PPh3>12 to give (q-cyclopentadienyl)(7-tetraphenylcyclobutadiene)cobalt246.
X-ray diffraction data has been
used to determine the crystal and molecular strilctures of
(7-cyanocyclopentadienyl)(?-tetraphenylcyclobutadiene)cobalt, (7-iodocyclopentadienyl)(17-tetra~henylcyclobutadiene)cobalt and (7-1,2-diiodocyclopentadienyl)(7-tetraphenylcyclobutadiene)cobalt.
In these compounds the cobalt atom was sandwiched
between parallel Ij)-cyclopentadienyland ?-tetraphenylcyclobutadiene rings which were planar.
The perpendicular distances
from cobalt to the plane defined by the five- and four-membered rings were 1.68 and 1.70 8 respectively.
The phenyl groups
were slightly bent away from cobalt with respect to the plane of the cyclobutadiene and they were twisted about their respective axes by an average of 35O in a propeller configuration 247. The borabenzene sandwich complex (13.4) when treated with diphenylacetylene in a sealed tube for seven days at 150' gave (~-l-methylborinato)(3_tetraphenylcyclobutadiene)cobalt (13.5)248.
King and 'co-workers have extended their investigations
G
!3-Ke
0
6 0
l
13.4
13.6
1305
of macrocyclic alkadiyne-transition metal complexes to include the complexes (y-C5H5>Rh(alkadiyne) which were formed by heating (?7-C5H5)Rh(CO)2 with alkediynes in cgclooctane. Five alkadiynes were used and
in each case intramolecular
transannular cyclization was observed to give the tricyclic I7-cyclobutadiene compounds (13.6; m = 5, n = 5 and 6)24g. References
p_ 288
m = 4,
n = 4, 5 and 6,
278
-Harder, Dubler and ?/erner have reported the preparation. and characterization of the trinuclear cobaltocene analogue The crystal and molecular structure of
(14.r>25°.
F ) was determined by X-ray diffraction. "7-c535'co~-c5'y41 B9C2-11
The species crystallj_zed in the centrosymnetri~ monoclinic viittr a = 10.02, b = 10.Y9, c : 14.55
space group
E2r/c
p=
v = 1585.2
98.57O,
if and Z = 4.
8,
The molecule was
z,vj_tterionicand was formed from a cobalticinlum cation and a p9CZH12]bond Wth
anion :lhich were linked via a carbon-carbon
concomitant loss of a terminal hydrogen atom from
each s;;ecies to give the molecule (~-C5!4)C~(?_G5~f~.BgC2~ll)2~1. Cobaltocene isolated in neon, argon 2nd krypton matrj.ces :;as studied by ES? at 4.~~ i-.:. Zarlier results were also considered and it was concluded that the orthorhonbic splitting Paraneter
S (measuring
the deviation from exact five-fold
symi:etry) increesed in the host series ruthenocenenickelocene ( neon < argon < krypton from lob cmi1 , to approximatei$- 3550 cm-1 . iZo
'The 13C iGE? spectra of (7-indenyl)chromium
tricarbonyl, bis(q-indeuyl)iron,
bis(q-inde_nyl)cobaIt
279
hexafluorophosphate and analysed
with
and bis(t?-indenyl)nickel reference
In the case of the nickel shown
to be a trihapto
-deuteriun
exchange
complex,
The rate
in cobaltocene
reaction
ligand
in basic
state
group
Was
of hydrogen-
I
media was slower It was concluded
tetrafluoroborate.
the oxidation
recorded
bonding,
the 7-inaenyl
ligand 253 .
than that of cobalticinium that in this
to the metal
were
of the cobalt
aton
was important 254. The nitrile
heterogeneous_electron
interface
dicarbollide
for cobaltocene,
analogues
a.c.
polarography.
with
the molecular
Laveron
and Dabard
The rate
Q 0
have investigated oxidation
9
I \
correlated Hurr,
the -chemical (02, or
of the cobalt
complexes
In eac!l case the cobalt-with aqueous
(14.2) 256 .
acid
l,ll-Ciethyl-
a1
Ql0
co
6 0
14.2
pF6R2 14.3
R2
cobalticinium
cation
to a mixture
and the diacid agent
were
using
+
0 in acid
kinetically
obtained
The oxidation
in the complex
cc
E
and their
of the complexes 2%.
structures
iciniurl ion vias obtained. first order
nickelocene
constants
it1 = g2 = ii,Xe, C02We).
(14.2;
at a mercury-aceto-
has been investigated
ii") and electrochemical
was
transfer
with
of the diketone
(14-3;
nas a nitric
References*.288
was oxidized
potassium
(14.3;
X1 = R2 = CO,ii>.
acid-potassium
perman&anste
ii' =.R2 = CO&)
'::henthe oxi6izing
p-ermanganate mixture
then
-m
.-
-.
the &ed_ac&l. was
rpcp2co-
by
(14.3;
salt
formed _- in _ addit%on_to Geiger
.
carboxy
the
electrochenical
ion in dimethbxyethane.
first metallocena
reduction
The anion
was stable
ethane molten
l.,l*-bis(carbethoxy)cobalticiniuz
equimolar
amounts
methyl)benzene
gave
poly(cobalticinium-l,I';
decomposition
salts
occurred
hexafluorophosphate)
hexafluorophosphate)
ivere made to prepare
cobalticiniumdiamine
of
f-diylcarbonyloxymethylene-l,l+-
-ghenylenemethyleneoxycarbonyl Attempts
The reaction
and l,k-bis(hyciroxy-
-diylca$oonyloxydecamethyleneoxycarbonyl and poly(cobalticinium-1,l
in dimethoxy-
hexafluorophosphate
of l,lO-decanediol
the polyesters
anion,
of then cobalticinium
but deco.mposed in acetonitrile 2.58.
with
Rz = CO@
two products 57.
previous
the
ha.4 generated
RX = COXe,
respectively.
polyaLn.ides from l,l'-dicar*~oxy-
by melt
and sure
techniques
.
but extensive
,;olgamides could not be
isolated258j.
15.
cobalt-carbon
Cluster
i4ethylidynetrFcobalt important
Frodusts
Com;>or>nds nonocnrbonyl
from the reactions
and chlorosilanes. 4 de;;endcnt on solvent basicity,
kiaCo(CO)
and the cobalt and cobalt
carbonyl
carbonyl
The
derivatives of cobalt
course
the nature
species.
yxerd thz.
carbcnyl
of the reaction
or was
of the chlorosilane
-Thus silicon
tetrachloride
or lTaCo(CO)k in L'HF or dicthyl
ether gave
Li_d~netrLcobalk
Cl.SiOCCo-(CO>9 259. o<,e-Unsaturated methyl3 3 nonacarbonyl complexes (15.1) viere gregared
by the~reaction
between
the trichloride
vinylic 05
the
trihalomethyl methyl
-yropionic
dicobalt
derivative
derivative
anhydride
cave
(15.1;
octacarbonyl (Scheme
ond the ap;;ronriate
15.1).
ProtonaEon
R ' = ii,R2 = Je) vith
the hexafluoro>hos;hate
iEP?b-
salt of the
281.
BIC!I=C
x2 <+-
3J27-. CO(C0)
ELF
CO$r,O)~
(oG)3co
“X3
Co(C0)
x =
Cl,
3
!3r
15.1
3
Scherle 15.1
carbenium
Treatsent
iozi (15.2).
gave ?SeOCC(We)2CCo3(C0)Q
_
I~?HC(ic~e)2CCo3("0)9260.
of this salt with
and treatnent The
?
M.th
aniline
-cycloheptatriene .
methanol gave-
complex
(15.3) was formed by heating dodecacarbonyltetracobalt and The physical properties of the
cycloheptatriene in hexane.
complex shot:fedsome resenblences to (7-cyclohe>tatriene)The preparation of the cobalt chromiun tricarbonyl 261 o cluster acylium ion (15.4) from carboxymethylidynetricobalt . nonocarbonyi and its esters with sulphurlc acid has been
resorted
with
a~16 ZschSach .
15.4
15.3
15.2
full experimental
details
by Seyferth,
The reacti-zns of th e-acgliu.~ ion
Hallgren
(15.4) M_th
alcohols, phenols, -ti;io?_s,amines, Grignard reagents and organometallic compounds which were oSutlined-in the prgliknary .
References p. 288
-.~
- :;
282
communication 263 have been extended and described in detail 262 . The crystal and molecular structure of tKe mixed crystal q-g-
and g-xylene)enneacarbonyltetracobalt
X-ray analysis.
was’ determined
by
The unit cell data were, space group g2l/g
with a = 10.03: b = 9.86, c = 20.24 8,/3= 96.4O, B = 4.
The
unit cell data for (7,benzene)enneacarbonyltetracobalt viere, space group RJ with a = 9.79 8,
= 82.95O, z = 2.
Both the
structures consisted of a tetrahedral cobalt cluster with
to the arene moiety, while the other
three are each bonded to two terminal and two bridging carbonyl groups.
The aromatic rLngs shoaed no significant distortion
frop local six-fold sywetry 264.
Charge delocalization in
the cluster carbenium ions (15.5;
H = &I, 13e, Ph) has been
investigated by 'E and '3L NX!? spectroscopy.
The results
suggested extensive charge delocalization from carbon to cobalt and compsrisons \'rithferrocenylccarbeniuLqions indicated that the cluster crttions were stabilized at least as effZciently as their ferrocene analogues 265 .
Differences
between tke mass spectra of the conplexad and free tetrahydronaphthalene licand have been observed. CCbRit
The ligand in t:.e
complex (15.6) loses sclal.1 r,eutral molecules (IZ2)with
aromatization Vfhiie atomic hydrogen is lost from the free liEand The results are expktined in terms- of the activation
energies
of possible fragmentation rou tes of the molecular ion266 .
_
283 T'ne reaction of cobalt complexes of the type [YCC_03(CO)J (Y = Cl, Me, Ph), ~(~-CgHs>fjiCo3(CO)~[sCo3(CO)~, and cco~(co)lJ
iwith isocyanides,
(R = Me, But), was
The reactions took place under
studied by Uewaan and Manning. mild
RNC
[SCozFe(CO)J
conditions and up to five carbonyl ligands were displaced
by isocyanide with retention of the XCO~ or SCo2Fe cluster (X = C, Ni, S or Co).
The structures of the products were
discussed 011 the bases of their infrared spectra 267. reduction of the acyl cluster compounds (15.7;
The
R = alkyl or
aryl) to the res:)ective alkyl or aralkyl compounds (15.8;_ R = alkyl or aryl)
was
achieved
under
acid
conditLons,
triethyl-
and trifluoroacetic acid in TIE', yields vaere good
silane
The secondary alcohols (15.9;
(67-?2+).
R = alkyl or aryl)
vere obtained shen t2;e cluster ketones (15-7)
were reduced
with triethylsllsne in boiling benzene folloued by sulphuric ,268 903~ .
acid and hydrolysis, yields varied between 46 and and his co-Trrorkers have continued
Seaferti;
investigations
Arylation
compounds. with
of nethylidynetricobalt
disrylmercurials
Y%? proceeded yields
were
:;hen the reactions
monoxide
irreversible
degradat%on.
aryl groups
hnlogeno-
contrast, References
p_ 288
alkylation
The
ylere carried
material
Zourteen
or
out under
the reversible and
aryl
its
com~~lexes
way in yields of up to 96%.
(Ar) introduced
Introduced,
in benzene
temperature.
were
methox:=-, methyl-,
and a~mlno-;: henyl and perfluoroghenyl.
scroup was also 0
cluster
nonacarbon/l
-;rhichsuppressed
from the starting
(15.10) ‘Nere formed in tWs The
halides
at the reflux
of c.rrrbonmonoxide
loss of cnroon subsequent
and arylmercuric
maxFmised
an atmoqhere
nonacarbonyl
of methylidynetricobalt
in good yield
their
althought
reactions
with
in rather
The
ferrocznyl
low yield.
dialkyluercurials
and
Zy
. ,284
.c&ytiercuric Arylation
halides were slow and gave poor yields of products.
of the
halogen0
cluster
_ Cl, Br, I> with-diphenylmercury structurally
related
compounds
Hal =
(Sill;
The
was also achieved.
acetylenedicobalt
hexacarbonyl
cluster
)3
3
(OC
COGI 15.10
15.9 compound
was
the mono-
phenylated
(15.12)
-:G_thdiphenylmercury
and di-aryl
(15.13)
aechnnisms
for these arylations
(ccric salts)
and thermal
carbonyltriccbalt the acetylenes uere
16
I
formed
radical
and ionic Oxidative
of th= methylidynenona-
IKCO~(CO)~
(I? = Ph, CE2Ph)
It was thought
by the coupling
in yields
were discussed 269_
degradation
compounds
IKE.SH.
derivatives
Alternative
of 21% and lO$ respectively.
to give both
gave
that these acetylenes fragments 270 .
of the tzo methinyl
07-c;i-i5~& Sarnr-tt has reviened
survey
vf.asdivided
oundin;,
into the
ring-addition,
reacticns _
of 19?327!-. nickeloccne disarboxylate
the chemistry
ring
LYhe literature
following cleavage survey
of nickelocene.
sections: and
structure
finally
was complete
The
ligand
transfer
up to the end
Undergraduate experiments for tke preparation and the reaction
of nickelocene
have been described
The reduction
of
with
lithium
of
dimethylacetylene
272 . b:r i3arnett-
(7-S5--5 77)I$ilJCwith
and
alumioiun
285
hydride-alu:r.iniunchloride gave paramagnetic and some nickelocene.
The structure of
[(~-C5-Y5)IJi]4H3
'[(ll_c,H5)Ni] 4H3
was shown to consist of a slightly distorted IJi tetrahedron The hydrogen atoms lay over 7-C5H5 groups at the apices. 273 three tetrrhedron faces . The X-ray structure analysis of
with
the trxple-decker sandwich complex (16.1) h&s confirmed the previous proI;osals based on other evidence,
The three
ligands and tzo nickel atoms are colinear with staggered cyclopentadienyl rinss.
The average nickel-carbon distances
for the two terminal rings are 2.99 and 2.08 2 and for the bridging ring are 2.13 and 2.16 8.
These bond distances are
consistent with the substitution patterns of the complex (16.11 with Lewis bases274.
Court and ii'err:er have presented 'H NKiR Ph
Sal
PII
evidence to support an ionic mechsnis:::for the formation of the triple decker sandvrzch (16.4) from nickelocene.
A solution
of nickelocere in anhydrous hydrogen fluoride contained the ring-protonated catLon (16.2).
Addition of boron trifluoride
to the solution gave the cation (16.3), isolated as the bro:'ln tetrafluoroborate.
The ion (16.3) attacked a further
molecule of nickelocene to form the triple-decker complex (16.4).
Although this route to the product-was favoured by
the authors, the alternative route through attack of the diene conplex (16.2) on nickelocene was not excluded275. References
p_ 288
266
BF4-
Ki
0
6
16.1
The cationic complex (16.5) was converted to the neutral olefin complex (16.6) on treatment with methoxide ion in methanol.
Abstraction of methanol from this product gave
the 3-ally1 compound (16.7).
The 1H iWR spectra of these
complexes y;ere discussed with particular reference to their stereochemistry 276.
The reaction between nickelocene and
dimsthylketene has been reinvestigated by Young.
The orange
solid obtained by miring the reactants in benzene was first assi,'ned an-complexeci lactone structure by SatG, Ichibori znd Satoz78.
It has now been reassigned as the structure (16.8)
16.3
.
16.4 -.
. _--_._ .
__
_-
__ --
287 formed by cycloaddition of one ketene molecule to a cyclopentadienyl ring; of nickelocene followed by insertion of a second ketene molecule into a nickel-carbon bond 277.. The reaction of nickeloceJle v.4th PBu3 or Ph2PBu in hexane gave the complexes h'i(PBu3)4 and Ni(PPh2Bu)Lc respectively.
A similar reaction rlithRPBu2 (R = Ph, E-tolyl)
gave the complexes (7-C5H5)Ri(RpB~2)227g. combined with Ph2PCS-t-Bu nickel complex (16.9).
Xickelocene
to give the 3-cyclopentadienylThe tertiary phosphorus atom in this
molecule was shown to be uncoortiinated, by quaternization ivith Rickelocene was attacked methyl iodide and ethyl bromide 280 .
+ 1 iii
0
@
Ri
by
K_ I -:.
-I-IeO!!
111
I 0
0
16.5
4
ONe Obie'
A-
*
16.6
bis(trifluoromethyl)diazomethane
16.7
to give a 1:2 adduct
with a nickel-cyclopentadiene bridge (16.10)~'~.
.
The kinetics of llgand exchange between nickclocene and (a) lithium cyclopcntadienide (XC +=.)a (b) the tetramethylethyleneciianine adduct of LiC5D, and (c) bis(v-cyclopentadienyl)/ manganese , have been studied, For reaction (a) the rate law suggested that exchange proceeded by two paths.
The first
path involved rate determining association of nickelocene and LiC5D5 and. the second involved similar association of Referencesp.288
.
dimer was forty
time_s as reactzve
formed
a clathrate
did not when
it-accompanied
stabilized
with a th$n
thiourea
All
ferrocene,
degradation
o_f nickelocene
costfng
but nickelocene
attempts
3.
were unsuccessful2' against
rkadfly
Ho_wever nickeloc;ene aas -included
form such a complex.
*with ruthenocene were
with
least
Ferrocene
as the nonomer2'c.
complex
at
form clathrates
Polypropylene
by ultraviolet which
behaved
films
radiation as an energy
agent 284.
transfer
16.10
16.9
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