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Thallium
467
THALLIUX ANNUAL
Hideo
SLiR?'EYC'XEFIXG
Kurosawa
Department Suita,
This
and Rokuro
of Applied
Osaka
THE YEXR
Okawara
Chemistry,
survey
will
deal with
and spectroscopy
compounds
containing
1) reviews,
2) synthesis,
of organothallium(II1)
thallium-metal
organothallium(II1)
compounds
bonds,
4)
compounds,
reactions
and 5) thallium(I)
3)
of
compounds
Reviews Review
articles
on O-organometal
(1) and on the biological organometallic compounds
2.
University
Osaka
(JAPAN)
structure
1.
1971
compounds
of related
Synthesis,
aspects
hydroxylamines
and effects
(2) included
surveys
and oximes
displayed
by
on organothallium
interest.
Structure
and Spectroscopy
of Organothallium(III)
Compounds The reaction been
found
3TlSCN
of TlSCN
(32 to yield
i- 3FIe3Al
with
trimethylaluminum
[Me2T1][bIe3A1NCS]
in toluene
according
to eq.
has
1.
-,
[Ele2Tl][Me3AlNCS]
+
2Tl
+
2Me2AlSCN
* Thallium, Annual Survey covering the year 1973 see J. Organometal. Chem., 79 (lg74)1-?6. References
p. 489
(1)
468
The
crystal
structural
the presence
of the Al-X
be a consequence
environment
essentially
octahedral
distance though
(Fig. 1) with atoms
and two Al-methyl
carbon
atom
C-Tl-C
interacting
lying
to
of the thallium
in the cation
a linear
was
unit
with
(Tl-C
thallium,
at 3.13 i from thalliu
in character,
atoms
revealed
was believed
requirements
of the thallium
electrostatic
(UC._ ._ 7
in the anion which
two sulfur
2.15 i),
largely
bond
of the compound
of the coordination
The
atom.
determination
at 3.15 i from thallium.
,_.C(Al)
--TiS ___--_ 1 ==_‘S C Fig.
The
crystal
1
structure
Kristallogr., Tl-C
87
and Tl-Cl The
The
reaction
from
compound
been
spectra
acid. Group latter
the reaction
is ionic
with
discussed
Group
analogs
compounds,
were
measured
I was
suggested
compound
and methylsulfonic
an equimolar
I (6).
and compared
spectra
dimethylthallium
The same
IIIb organometallic
The vibrational
(see 2.
(4); the observed
and the IR and Raman
with
Me2T10(0)PF2
refined
SO5 afforded (5).
in nature
chloride
and 3.029 i, respectively.
of Me3T1
Fle3T1 reacted
of I were
IIIb
are 2.139
of Me3T1
to afford
for the other
370) has been
Me2T10(0)2SBie
reported.
HO(0)PF2
(1934)
distances
methylsulfonate, obtained
of dimethylthallium
and. assigned to be
ionic
spectra
have
of
('H, "F,
31P)
corresponding
derivatives
(IR and Raman)
also
acid.
quantity
The NMR with
was
data
of phosphoric
of I and other (7).
Unlike
in nature.
the In
469
another
study,
2/l ratio Ehemann
StSTl
and Dehnicke and
[?Ie4S]CN and
the vibrational could
and
obtained
(Et2T1)2SCN,
spectra to the
compounds,
former
and a linear
IR spectroscopic
R2TlXCS
(R= Me,
Ph),
[Ph4As][?le2T1(NCS)2]
(10).
From
the frequencies
band
state,
in solution,
derivatives character a Tl-SCN
study
it was
suggested
are isothiocyanates in the Tl-KCS
bonded
dimethylthallium l/l Adducts
bond,
compound_ moiety
with
(salicylideneiminato)nickel(II) amine)nickel(II) group
in Italy
in the solid electronic
state
spectra
as well
intensity
vibrations
of the u(C2-K)
the diorganothallium
a certain
amount
of ionic
is essentially
configurations
the complexes
been
A possible
has been
and PhTl(XS)2,was
(Nisalen)
(Xi>lEA,) have (11).
deriv-atives,
of the
also discussed. with
of PhTlCl2
bridged
compound.
r;hereas PhTl(XCS)2
Possible
were
Tl-F-T1
of the NCS group
that
and bis(R-mercaptoethyl-
synthesized
structure
suggested as magnetic
N,N'-ethylenebis-
by a research
of these
on the basis measurements
new
(Fig.
L= S for PhTlC12.NiPlEA2
References p_ 489
2
compounds
of IR and
L= 0 for PhT1C12.Nisalen
Fig.
of
a CSv point-group
of the thiocyanate
and the integrated
of >IeSTl
On the basis
in the latter
Another
in the solid
(9).
of these
I\'asassumed
(8).
compounds
[~le,X][(bIeST1)2F] from the reaction
of Djh symmetry
reported
respectively
organothallate
[?Ie4N]F in hot toluene
be assigned
system
to react l;ith E12NCX in l/l and
reported
to give Et2TlNMCN
[Me,X][kIe3T1CX] with
was
2).
470
These Italian authors also reported (12) that the l/l adduct formed from PhTICIZ
and
N,N'-ethylenebis(acetylacetoneimine)
dissociates into the parent components in methanol, as suggested by examining the IR, electronic
and
PMR
spectra
as well
as
the
conductivity. Bis(trimethylsilylmethyl)thallium (II, TlClS
x=
Cl;
or
III , X=
TlBr
Br)
(13).
have
been
Several
halides, prepared
other
(E-Ie3SiCHZ)ZTlX
from
hle3SiCH2Li
and
trimethylsilylmethyl
derivatives of Tl(II1) were synthesized starting from II as shown in Scheme 1.
Scheme 1 * TIOOCiPr RZTICl
RZTIOOCIPr
>
v
II I
1
Br2Py TIOOCiPr
[RTClBrl
Eg(OOCiPr)2
RT1(OOCiPr)2
>
VI JIeqSn I
1
TIOOCiPr
bIeRTlBr
MeqSn
MeRTlOOCiPr
7
VII
IV (R= Me3SiCH2)
Compounds
II,
III
and
in marked
contrast
to
This
has
Comparison
been
IV were the
attributed
found
polymeric to
the
to be dimeric in chloroform, dimethylthallium halides.
bulkiness
of
the
Me3SiCH2
group.
of the J(Tl-H) values in III and IV as well as in V,
VII and Me2TlOOCiPr suggested that the electronic effect of the Me3SiCH2 is very similar to that of the methyl
group.
That
VI
is
471
much
more
stable
or ethyl
analogs
toward
reductive
also was
decomposition
interpreted
in terms
than
its methyl
of the steric
effect. Mono-
and diarylthallium
di-t-butylphenol
VIII
stable
IX-XI
compounds
in polar
compounds
reacted
solvents
(14) as shown
to yield
with
2-amino-4,6-
diamagnetic,
in eq. 2-4.
(2) IX t 2
KHZ
OH
ArTl(OOCCF3)2
Ar,
,OTl
> Ar'
or Ar2TlOOCCFS
N
(3)
'OL X
(4)
I
-NH4X
Ar=
Ph, p-tolyl,
2,4,6-Me3C6H7,
E-C~C~H~ X= Cl, Br
On the basis
of the ESR measurements
PhT1(00CCF3)2
and VIII,
as
and XIII was
such
References
XII
p. 189
the existence suggested.
of the reaction of paramagnetic
mixture
from
intermediates
472
Ar,
Ar,
Tl
X
Tl
X'
X' H XII
XII and XIII chelate
Scheme
XIII
further
compounds
reacted
as shown
with
VIII
in Scheme
to form the eight-memberec
2.
2
VIII
f
XII
VII I
c
XI I H2 S
Tile IR and proton terms
of their Kumar
and Cc&,
et --
NF:R spectral
corresponding
data of IX-XI were
discussed
in
structure. al. extended
indenylthallium CgH7)
11
with
KX
the chemistry
derivatives.
Thus,
of cyclopentadienyl-
treatment
(X= CE, NCO, NCS, N3) afforded
organothallium
pseudohalides
(15).
of R2TlCl the IR studies
(R=
413
.indicated species,
these R2TlH
compounds (R= C5H5,
(16) from the reaction with
NaH
in THF.
2200
cm-'
potassium
values
salt
formed
atoms
C8H8TlCl
reported.
in THF
resulted
+
was
reaction
methane
of
in the presence
trienylthallium The
(C5H6N)2T1C15
in the formation
identified
compounds
with
of C8H8TlCl
states
+
NaCl
l
C7H7T1C12
with
the
in which
(eq. 5).
(Z= NMe,
in dichlorocyclohepta-
NC6H40Me-2,
or aldimines
as shown
in eq. 6.
The presence
of the quinonoid
solution
was
shown by the electronic
(5)
(18).
the aldehyde
with
0) were.-
Et2T10H tautomer
(19) in
spectra.
CH=Z OTlEt *
References p. 489
of the
'10H8
afforded
by boiling
structural
chloride
as (C8H8)2T12,
prepared
The
reported
W&$WIl,
cycloheptatriene
o-Et2T10C6H4CH=Z
CH=Z OH
and
THF ______3
of triethylamine
dichloride,
also
thallium(III)
thallium(I),
l/2 (C8H81 2T12
The
authors
are in +3 and +l oxidation
NaC10H8
to be prepared
or that of R2TlCl
These
by the reduction
of naphthalene
two thallium
Et3N
hydride
of 2105 cm -' for R= C5H5
of cyclooctatetraene
the product
sodium
with
claimed
of cyclooctatetraene
metal
salt
Ofganothallium
has been
of R2T1BH4
v(Tl-H)
reduction
potassium
while
C9H7)
for R= C9H7 were
(17) that with
to be ionic.
Et2T10H/
study
of diethylthallium
2,-----
salts
(6)
of polynitroalkanes,
474
CH (Mc12) 3,
thallium
CH2(NO2), iodides
electrolyzing
R,TlI i
of K2HP04
separated
with
Various
using
a ceramic
thallation
methyl
method,
diaphragram
trimethylsilanes
as in eq.
FIe3SiC6114S
+
synthesized
3-Cl,
3-Br,
also
found
to react
FIe3SiOOCCF3
and CF3COO?fe, probably
report
The proton
(Tetrahedron
above
XYR data
were
(22) using
(23) that
be isolated
Letters,
?!e3SiOOCCF
x-
the formation
(71
3
2-F, 2-Cl,
acid
work,
of
for the arylthallium A reexamination
and Tl(OAc)3 adduct
does exist
of the
on the reaction
of
now has
XIV, which
could
not
as a well-
material.
T~(OAC)~ ------+
COOH
aryl-
with Ye Si to form 4
(1966) 1363)
the oxythallated
in the former
characterizable
+
3-CF 3, 3-(Me,
reported.
S-norbornene-2-endo-carboxylic confirmed
reported
4-CF 3, 4-Ph
was
obtained
some of which
CF+OOI! p-_-3
Tl(OOCCF3)3
Tl(OOCCF3)3
compounds
in aqueous
7.
S= I!, 3-?Je, 3-F,
>leTl(OOCCF3)2.
by
(21).
SC61i4T1(OOCCF3),
2-Ne,
prepared
ahd a Pt-riire anode
by the previously
now been
Diorgano-
iodides
bistrifluoroacetates,
obtained
have
and ethyl
a Tl cathode
arylthallium
not be readily
(20).
reported
(R= CII2CH2CZi. Ffe, Et) were
B-cyanoethyl,
solutions
could
and ?!eCII(N02), was
(81 0
XIV
475
XV and XVI were
obtained
similarly
(eq. 9,lO).
(9)
4
Tl (OAc) COOH COOH
(Ac0)2Tl 3
@? 0 O
13 C MR reported
data
nuclei
for a series
by two groups.
and chemical
coworkers
(24).
chemical
that
withdrawing
on chemical detailed
In a related
shifts
description
NMR spectra
of the Tl(II1)
couplings
5.
was
Compounds
reported
these
electron-
(2.5), substituent were
derived
(26).
Containing4halliurrmetal study
Tl(1)
given.
tetramethyl
The
13C
ester
The pattern contact
of 13C-T1 mechanism.
Bonds
on the stability
of both
was
a
of alkyl
shol+n.
of the Fermi
effects
after
assignment
group was
coproporphyrin
in terms
authors
on alkyl-substituted
of signal
and assigned
interpreted
derivatives
References p_ 489
derivatives, is a powerful
and
Kitching
and "F
constants
to the Tl(OOCCF,),
A comparative carbonyl
by
of 6J(13C-205 Tl) on the conformation
para
were
of coupled
the 13C data
study
of the method
were
205 Tl couplings
discussed
by Ernst
and coupling
side-chains
chelates
group
trifluoroacetates
The dependence
were
of the p-fluorophenyl
group.
arylthallium
of 13C_203,
of both
the T1(00CCF3)2
compounds
on the disposition
effects
On the basis
shifts
suggested
shift
XVI
of arylthallium
The range
the dependence
to be expected,
(IO)
COOH
F
of transition-metal
and Ti(II1)
was
reported
(27).
476
Tl[Co(C0)4] Scheme
3.
Scheme
3
Tl+
XVII was prepared
rcowx41,q
+
aq
by several
methods
as shown
in
Hg [Co (CO) 412
.
Y Tl
The new
compounds
W) have
been
with
T1N03
synthesized
or T12S04
and Tl[Mn(CO)3] where
nation
in water.
reactions
The existence
inferred
of the
+
by examining
latter
stability
4HMn(C0)3
of these
(eq. 12) was
M(C0)3Cp
M= Cr; XIX, M= MO, XX, FI=
was
of Na[M(CO)3Cp
of T1[Co(C0)3PPh3] the IR spectra
accomplished
through
the
reaction.
[Tl(OEt)]4
The
(XVIII,
by metathetical
has been
the formation
following
found
.->
Tl(1)
4Tl[Mn(C0)3]
compounds
to decrease
toward
in the order
+
4EtOH
(11)
disproportioX= COG>
(W>Mo>Cr)>Co(C0)3PPh3=Mn(CO)5~Fe(CO)2Cp.
3TlX
The
T1[M(C0)3Cp]
KOI41 3
Tl[Co
W
TlX3
corresponding
to undergo
T1X3
a reversible
a greate.r or lesser and the stability particularly
+
2Tl
compounds reductive
degree
(12)
were
characterized,
elimination
depending
on the reaction
of the TlX compounds,
promoted
by light.
process
and found (eq.13) conditions
such elimination
being
to
477
c-
TlX3
TlX
The reversibility
+
of this
Tl[Co(CO)4],[W(CO),Cp] CO2(CO)8.
Closely
stability
of Tl(1)
function
the pK,
,I,
PQ-0C6H4Cl) the reaction of pKa>5
of XVII
to eq. 12.
Behrens
XXII,
M= MO)
SnPh3),
shown
Similarly
SbPh3,
obtained
T1[Fe(C0)3NO]
anions,
X-
and from
give HCO(CO)~L
but T~[CO(CO)~L]~ PnBu3)
were
resulted
Tl[Fe(C0)4R]
[M(CO)~CP]~
(R=
In related
T1[M(C0)3Cp]3
and
to be a
obtained
and T1[V(C0)6].
obtained metal
were
L which
derivatives
AsPh3,
thallium
was
the
5 (L= P(OPh)3
T~[CO(CO)~L]
the Tl(1)
and coworkers from
carbonyls
those
and
(28) in which
is less than
and L, while
P(OEt)3,
complex
of such metal-carbonyl
compounds
form
according
work,
strength
the mixed
from T1[W(C0)3Cp]
appeared
of HCo(CO)3L
P(OMe)3,
COPh,
work
transition-metal
(L= PPh3,
CH2CN,
enabled
to be prepared
stable
did not
(13)
reaction
related
of the base
when
Thus,
X-X
(XXI, El= Cr; (29)
(eq. 14).
0
3PfCCO13CP12
+
2Tl
&
2T1[M(CO)3Cp]3
(14)
THF M= Cr, MO
The reaction XVIII
reacted
Treatment Addition
of
[Cr(C0)3Cp]2
with
of XVIII of iodine
solid with
with
KBr
excess
to give K[Cr(C0)3Cp]
[Cr(CO),Cp],
to XVIII
thallium
afforded
and TlBr.
gave XXI according
also afforded
XXI
XVIII.
to eq. 13.
(eq. 15).
0
3T1[Cr(C0)3Cp]
+
12-_,
T1[Cr(C0)3Cp]3
+
2TlI
THF Structure studied References
in sqme p. 489
and some detail
reactivities by Schussler
of T~[CO(CO)~] et al ---
(38).
XVII were The X-ray
(15)
478 crystal ionic
structural
solid
discrete
determination
composed
close
are consistent
with
solvents
of high
abilit)- (water, Co(CO),,
while
moieties
DXSO,
ability
the presence
of tight
of covalent
to react
with
crystalline
Tl[Co(CO)4]
The reactions
which
were formed
InBrS),
CoC12.
The
study
was
extended
was
synthesized
from
with
lithium
VT1
The reaction
of this
compound
halides
Unlike
significant
to afford
found
very
(eq. 16).
the other
metal
f
with
IIIb
X-Y3 compounds
of type ?1C02Brj(Co)6
the cobalt
LIIb metal-tin (32).
(161
of the Group
or clusters
and Oliver
4FIejT1
the formation
in CHzC12
with
XVII was
observed.
chlorinated
on the Group
+
allowed
were
and rieak
WCoCW,12
(31).
merely
by Keibel
In
into Tl+ and
consistent
ions with
in solution
(BXS, AlXS)
TlClS
bonds.
constant
IR spectra
(
of Co2(CO)8
adducts
which
[(PhCU2)Ph3P]{Tl[Co(Co)517j
Co(W);
investigated
(GaBrS,
3Li
bonding
atoms
dissociates
or triple
dissociated
*
nor are there
covalent
of lox dielectric
ion-pairs
Tl-Co
is extensively
metals
D?.!F),the compound
(TflF, CH,C12),
are no
and good coordinating
[(PhCHZ)Ph3P][Co(C0)41
air-sensitive which
of strong
constant
in solvents
state,
betrceen Tl and other
the existence
dielectric
is an essential
There
ions.
in the solid
distances
coordinating
amounts
that XVII
of Tl+ and Co(CO),
Tl[Co(C0)4]
any particular
showed
carbonyl
bonded
to
compounds
In this work,
Li[Tl?le4]
and FieSTl (eq. 17).
3Li[Tl!Ie4]
varying
amounts
of Li[T1(>le3Sn)nFle4_n]
(17)
of Me6Sn2
(n= l-4)
(eq. 18).
479
Li[TIFleq]
+
nNegSnq
>
Li[T1(NegSn)nEle4_n]
SIR
Proton
analogous The 3
for
factors shifts
4.
in the
vas
were
of
compounds Ga,
afforded
of
(C6FS)2T1S
SAu(CoFS),L with
resulted
in no
tion was
observed.
of
TlS
for
reported.
'J(Sn-II),
'J(Tl-II)
of both _‘Iand n.
and
The
and the chemical
Br,
I) with
Ph,
A possible
Analogous SOS,
intermediate
x;as postulated
as
shown
SAUL
reactions
O&z,
but
'(L= PPhS,
SCM,
PPh3+)
substitu-
ligand
for the reactions
belot;.
CoF5
also
reacted
(34).
The
the interaction
In this study
EtZIIg7 was
probably
(eq. 19).
\ C6F5-Tl-X // fr-Au
or
with
PtC1Z(PEt3)z
PtCl,(PEt3)iTl(C6F5)2Br
respectively
ion
(18)
been
.&I(I) to Au(II1)
C6F5-T&-S-Au-L / Br
surface,
have
(35).
(Y= C6FS,
'gF5,
to study
Sn
Compounds (S=
and
Y‘AuPPhS
oxidation
S= halogen
to afford
4
as xiell as
in the couplings
Organothallium(I11)
reactions
(C6F5)?T1Br
In)
'J(Sn-H),
as a function
the changes
of
(C6FS),T1Br
with
(!-!=Al,
nNe
proposed.
Reactions
AsPhS)
tallium-tin
values
discussed
governing
The
such
Li[?I(!4e3Sn)>~e3]
variation
J(Tl-II)
of
data
+
or PtCl(C6F5)(PEt3),.Tl(CgFg)ZBr,
galvanostatic of Et2T1* shown
or PtC1(C6F5)(PEt3)2
method
ion with
to be formed
via the formation
has been mercury
employed
metal
(35).
on the mercury
of an intermediate
[EtHgTIEtlC
480 Hg Et2Tl+
The
+
Hg e[EtHgTlEt]+
formation
Ph2Tl(NCS)i-" distribution A 25 anion Ph2TlNCS
constants
exchanger
determined
of PhT12*
and aqueous
-for n= l-4, respectively,
were
at 25' from
and Ph2TlC
log B,= 2.3,
obtained;
Me2T10H
OH- catalyzed at 25O, it was
constant
exist
in aqueous
The reaction (n= O-3), which
characterized.
has been adducts
XXIV
by Me3SiNj
and Me3SiNC0,
X
20-22.
from
conditions
studies alcohol
constant
of the by
(dissociatio 1.5 M-l>
(37).
(38).
were
further
T~(OAC)~_~(N~)~
varying
investigated
isolated converted
amounts
of
With and to XXVI
and
respectively.
XXIII
X=Y=Z=N3
XXIV
X=Y=Z=OAc
xxv
X=N3,
XXVI
X=Y=OAc,
XXVII
X=N3,
such oxythallated affording
or
3.9, 4.7 and 4.8
ion pairs
by mixing
XXIII-XXV
Sephadex
PhTl(NCS)2
From
the system
and XXV were
(-JQTIYZ
several
with
can be generated
and Me3SiN3,
Dethallation
that both
solution
the
between
of diacetone
(dimerization
of olefins
benzonorbornadiene,
XXVII
concluded
0.090 M) and dimers
of Me2TlOH
Tl(OAc)3
decomposition
and
for Ph2T1(NCS)n1-n,
log B,= 0.1 and 0.6 for n= 1,2 respectively. specific
(19
Et2Hg2
(n= l-4)
KSCN containing
For PhT1(NCS):-n,
(36).
+
Tl
of PhTl(NCS)i-"
(n= 1, 2) were coefficients
+
C
various
adducts
Y=Z=OAc Z=N3
Y=OAc,
Z=NCO
was performed
compounds
as shown
under in eq.
481
N3
HX XXIII
or XXV
6
(x= F, Cl,
X
(20)
I, OH)
& -Tl(I) XXVI
A
XXVII
u
(21)
&:3 -Tl(I)
The
reaction
proceeded
(22)
of T1(OAc)3/Me3SiN3
according
with
to eq. 23 and
norbornene
or norbornadiene
24.
3
Tl(OAc) 3/Me3SiN3
HX/H20 \
A full account
>
of the study by Uemura
thallation
of acetylenes
appeared
acetylenes
$th
in acetic
acetoxythallated
T~(OAC)~ products
-et al. on the acetoxy-
Treatment
(39).
acid yielded
of alkylphenyl-
two isomeric
trans-
(eq. 25).
Tl(OAc)3 PhCZCR
> T~(OAC)~
Ph 'C-C' AcO/
'R
References
p- 489
Ph,
OAc c=c/
(AcO)~T~'
nB~
(25) 'R
XXIX
XXVIII R= Me, Et, "Pr,
+
482 Heating of
XXVIII
and XXIX
PhC(OAc)=CHR
The same
in acetic
and PhCH=C(OAc)R
compounds
hydrogenolysis
also were
of XXVIII
showed
the hydrogen
from
sequence
Scheme
the solvent, (Scheme
deuterium
group
the following
4).
,Tl(OAc)2
BH;
Ph,
c=c ’
f
experiments
suggesting
7'
AcO /
solvents
of the Tl(OAc)2
4
Ph,
from
in protic
labelling
from NaBH4,
3
Me
_ c-c
BH3 ‘=-0
,Tl\
&Me
ROH
H
Ph
> -HTl(OAc)
2
-
0' 'Me
AcO/
'CZC' AcO'
'Me
-BH3(0R)
Treating
XXVIII
with
CuX or CuX2
CN, SCN) with
retention
prepared
oxythallated
some
and investigated adducts
reacted
the corresponding good yields
adducts
the reactivities with
copper(I)
alkyl
gave PhC(OAc)=CRX
of configuration.
halides
These
of styrene of these
halides
(X= Cl, Br, authors
I,
also
and a-methylstyrene
adducts
(40).
and pseudohalides
and pseudohalides
The to affor
in moderate
to
(eq. 26, 27). T1(OOCRz)3 >
PhCRl=CH2
PhCR1(OR3)CH2Tl(OOCR2)2
(26
R30H
RI=
H, Me; R2= Me, iPr, nBu,
iBu
;
of configuration.;
products
NaBH4
for replacement
not
in the formation
retention
and XXIX with
In this reaction,
came
with
the principal
at pH 6-7. that
acid resulted
iPr; R3= Me, Et, nPr
483
PhCH(OR
cux
.3 )CH2Tl(OAc)2
B
PhCH(OR3)CH2X
(27)
X= Cl, Br, I, CN, SCN; R3= Me, Et, "Pr,
The effects KX were
of both
examined.
the nature A possible
halogenodethallation
The kinetics
in H2O/MeOH
Analysis
dissociates
of the oxythal,lated
PhCH(OMe)CH2Tl(OAc)2
The products
and its dimethylacetal. law.
proposed
The
for such
species
were
follows
parameters
adduct
XXX has been
identified
reaction
of the kinetic
into a reactive
of
is
of decomposition
(41).
and the addition
intermediate
reaction
and styrene,
Tl(OAc)3
of solvents
nBu
studied
phenylacetaldehyde
a first
indicated
RTlOH+
from
order
rate
that XXX
and a more
reactive
RT12+- (eq. 28).
RT~(OAC)~~
RTlOAc+
+ OAc-
cH2°
H+ RTlOH+e
RT?
(28)
R= PhCH(OMe)CH2
The
implication
determining largely The Tl(N03)3
References
step
depends
of this
is that
in the overall on experimental
distribution
of products
of the olefins
p. 489
study
RCH=CH2
the nature
oxidation
of the rate-
of styrene
by Tl(II1)
conditions. formed
in the oxidation
and R1R2C=CH2
in methanol
by has
484 been
studied
from
the former
formed.
(42).
With
olefins-
RIRZC=CH
the formation
log kl/k,= result
better
was
2-butene has
diols,
Taft
was
the
$
for
t 2:
R1COCH2R
;
by the equation,
that
the migration
of the
A possible
reaction,
preferentially.
and its dethallation
study
by Bertsch
and _cis- and trans-stilbene
but mono-
of
-!
p*= -4.
of the oxidation
the formation
formed
constants
that
constants
were
diether
the
of the rate
to suggest
In a related
only
(kl) versus
with
occurs
and RCOMe
CHZCl
RlR2C(OMe)CH2T1X2
examination
confirmed
compounds
~*(a~*-al*)
donor
R=
the ratio
to the polar
involving
discussed.
a careful
2'
led the authors
electron
sequence
When
of the RZCoCHZR1
(k2) was related
This
Both RCH(OMe)CH2OMe
with
of not only
and dinitrate
T1(N03)3
(43),:
2,3-dimethylin methanol
the carbonyl
esters
step
and Ouellette
of I-decene,
and dimethoxy
of the corresponding
e.g. _-
Tl(NO3)3 Me2C=CMe2
> MeOH,
2 Me3CCMe
+
Me2C -CMe2 I I OMe Oble
O0
(45%)
(3%) c
Me 2C -
CMe
I2
I
+
ONe 0N02
Me2C I ON02
(34%)
Stereochemical
analyses
stilbene
led the authors
proceeds
in a trans
of the products to
fashion,
believe e.g.
that
CMe
2
I
(291
ON02
(18%)
from
cis-
and trans-
the initial
in Scheme
5.
1
oxythallation
466
Optical
Jcemic
i3;:3
cl7
Product
TlX,
L-I!
R= AC, iIe, Et
OR X= Ok,
SOS
(S)-XXX11
OR
(S)-XSSIII methoxy-
Similarly, gave
optically
and ethokythallation-dethallation
active
facts
led the authors
XXXIV
cannot
purity
In other
wcrk
noradamantane XXXV
process
Scheme
to suggest
involves
of XXX111
XXXVI,
XXX111
that
to XXX11
an anti mode
which
to give
was
had been
a 60% yield
The
of addition.
with
prepared
cation
and that the
reduced
treated
allylic
when
S= NOS.
Z-methylene-
from Z-noradamantanon
of 4-protoadamantanone
7). ,Ok
7 Ol%
D1, D=rLl
\__
also
These
(R= Me, Et].
the planar
(R= Me, Et) was
(451, Tl(ClO,)S
and PhSPCH,,
(Scheme
ethers
be the sole precursor
oxythallation optical
allylic
of XXX1
TV rr,n , XzTlCH&
XSXVII'
487 0
-Tl(I)
423 XXX\-1I
The
formation
of XXSVII
intermediate position
involving
resulting
and a subsequent the fact that is treated different
was
assumed
to be a consequence
a cationoidic
methylene
from the exo attack These
dethallation.
the isomer
of SXXVII
tcith diazomethane conformation
in an axial
of II,0 L in osythallation sequences
is formed
in ?IeOH owing
bearing
group
of an
l
selectively
with
when
XXXV
to an intermediate
an exo cationoidic
methylene
of as in
eq. 30.
XXXV
CH,N:, - -> bleOU
study
A comparative Tl(III)
and Pb(iV)
products RCONe,
identified
from the Tl(III)
(R= C6HI3).
impurity
discussed
of decomposition Some organic
other
effective
studies
Tl(ClO4)3
in the presence
importance
of chalcones
(48), iodination of Tl(OOCCF3)3
include
came
distribution
of several
ways
adducts.
the synthesis
of g-quinols
The
and
compound
The product
oxidant.
of the application
rearrangement
oxidations i
in the last
by Hg[II),
(46).
RCH(OAc) CH_,OMe
of the relative
include
synthesis
in-methanol
and Pb(IV)
of the oxymetallated
synthesis
the oxidative
Chlorine
in the metal
in terms
of the oxidation
of 1-octene
i.
from Cl-
with
acetates
made
RCH(011e)CH20~!e, RCH(O\iejCH,OAc,
RCH(O>Ie)CHZCl
was
has been
of Tl(III)
compounds
of isoflavonoids with
by oxidation of benzene
Tl(xO3)3
to
through (47), an
of.E-alkylphenols
and mesitylene
(493, and iodination
with
by KI of
I2
488 arylthallium aromatic
bistrifluoroacetates
acids
Thallium(I)
derived
from Tl(OOCCF313
and
(SO).
Compounds
m- and p-Fluorophenylcyclopentadienylthallium(I) synthesized
19
and
F NMR
spectra
were
measured
in THF
have
been
(51).
The
chemical
shifts
were
compared
with
(M= alkali
metal) bond
and CL and o" values calculated thereof I R the respective values for MC3HqC6H4F-~(~)
and C5H3FeC3H4C6H4F-m(p).
ionicity
thallium(I)
has been
salt
previously
Commun.,
several
(1972)
TlOOCR/I2
the reaction
and coworkers
system
TlOOCR
and
yield
T12C2B9Hll
1178) has been (52).
was
obtained
utilized
for
the reaction
Thus,
with
Me2AsBr
extended
in organic 12 gave
their
synthesis.
study
of
in a 2/l ratio
the corresponding
+
TlOOCR
f
I2 v
(R= Me, CF3,
reactions
are regiospecific
of the products, A possible
of the use of treatment
Thus,
of alkenes
c-iodocarboxylates
::-c: I
iodonium
which
The
(53, 54).
3c=c;:
The
in THF.
(Me2As)2C2B9H11.
Cambie
._in high
to be 40-50%
arsacarboranes
3-R-3-As-1,2-C2B9Hll;
with
thallium-cyclopentadienyl
with RAsX2 (R= Me, X= Br; R= Ph, nBu, X= Cl) produced
T12C2BgHll
afforded
estimated
of 7,8-C2B9Hl12-,
(Chem.
synthesizing
The
offer
mechanism ion type
intermediate
AOCR
Ph)
and in conjunction
an alternative
involving
(31)
with
to the Prevost
an iodine-alkene and a Tl(1)
solvolysis
reaction.
s-complex,
species
rather
an than
a
489
Tl(III)-olefin
interaction
has been
of unsaturated
thallium(I)
carboxylates
IZ gave
a convenient
conditions
to the Survey
Solutions
various
reaction
e.g.T100C(CH2)nG=C( --
for iodolactonizatibn
with
under
neutral
(55).
Complementary
prepared
procedure
A similar
discussed.
Covering
of the 5-bromo-
by treatment solvents
These
to the unsubstituted
1973
or 5-chlorocyclopentadienes
of CpTl with
(56).
the Year
were
the N-halosuccinimide
5-halocyclopentadienes
cyclopentadienyl
cation
in
were
on treatment
converted with
SbF5.
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THALLIUX ANNUAL
Hideo
SLiR?'EYC'XEFIXG
Kurosawa
Department Suita,
This
and Rokuro
of Applied
Osaka
THE YEXR
Okawara
Chemistry,
survey
will
deal with
and spectroscopy
compounds
containing
1) reviews,
2) synthesis,
of organothallium(II1)
thallium-metal
organothallium(II1)
compounds
bonds,
4)
compounds,
reactions
and 5) thallium(I)
3)
of
compounds
Reviews Review
articles
on O-organometal
(1) and on the biological organometallic compounds
2.
University
Osaka
(JAPAN)
structure
1.
1971
compounds
of related
Synthesis,
aspects
hydroxylamines
and effects
(2) included
surveys
and oximes
displayed
by
on organothallium
interest.
Structure
and Spectroscopy
of Organothallium(III)
Compounds The reaction been
found
3TlSCN
of TlSCN
(32 to yield
i- 3FIe3Al
with
trimethylaluminum
[Me2T1][bIe3A1NCS]
in toluene
according
to eq.
has
1.
-,
[Ele2Tl][Me3AlNCS]
+
2Tl
+
2Me2AlSCN
* Thallium, Annual Survey covering the year 1973 see J. Organometal. Chem., 79 (lg74)1-?6. References
p. 489
(1)
468
The
crystal
structural
the presence
of the Al-X
be a consequence
environment
essentially
octahedral
distance though
(Fig. 1) with atoms
and two Al-methyl
carbon
atom
C-Tl-C
interacting
lying
to
of the thallium
in the cation
a linear
was
unit
with
(Tl-C
thallium,
at 3.13 i from thalliu
in character,
atoms
revealed
was believed
requirements
of the thallium
electrostatic
(UC._ ._ 7
in the anion which
two sulfur
2.15 i),
largely
bond
of the compound
of the coordination
The
atom.
determination
at 3.15 i from thallium.
,_.C(Al)
--TiS ___--_ 1 ==_‘S C Fig.
The
crystal
1
structure
Kristallogr., Tl-C
87
and Tl-Cl The
The
reaction
from
compound
been
spectra
acid. Group latter
the reaction
is ionic
with
discussed
Group
analogs
compounds,
were
measured
I was
suggested
compound
and methylsulfonic
an equimolar
I (6).
and compared
spectra
dimethylthallium
The same
IIIb organometallic
The vibrational
(see 2.
(4); the observed
and the IR and Raman
with
Me2T10(0)PF2
refined
SO5 afforded (5).
in nature
chloride
and 3.029 i, respectively.
of Me3T1
Fle3T1 reacted
of I were
IIIb
are 2.139
of Me3T1
to afford
for the other
370) has been
Me2T10(0)2SBie
reported.
HO(0)PF2
(1934)
distances
methylsulfonate, obtained
of dimethylthallium
and. assigned to be
ionic
spectra
have
of
('H, "F,
31P)
corresponding
derivatives
(IR and Raman)
also
acid.
quantity
The NMR with
was
data
of phosphoric
of I and other (7).
Unlike
in nature.
the In
469
another
study,
2/l ratio Ehemann
StSTl
and Dehnicke and
[?Ie4S]CN and
the vibrational could
and
obtained
(Et2T1)2SCN,
spectra to the
compounds,
former
and a linear
IR spectroscopic
R2TlXCS
(R= Me,
Ph),
[Ph4As][?le2T1(NCS)2]
(10).
From
the frequencies
band
state,
in solution,
derivatives character a Tl-SCN
study
it was
suggested
are isothiocyanates in the Tl-KCS
bonded
dimethylthallium l/l Adducts
bond,
compound_ moiety
with
(salicylideneiminato)nickel(II) amine)nickel(II) group
in Italy
in the solid electronic
state
spectra
as well
intensity
vibrations
of the u(C2-K)
the diorganothallium
a certain
amount
of ionic
is essentially
configurations
the complexes
been
A possible
has been
and PhTl(XS)2,was
(Nisalen)
(Xi>lEA,) have (11).
deriv-atives,
of the
also discussed. with
of PhTlCl2
bridged
compound.
r;hereas PhTl(XCS)2
Possible
were
Tl-F-T1
of the NCS group
that
and bis(R-mercaptoethyl-
synthesized
structure
suggested as magnetic
N,N'-ethylenebis-
by a research
of these
on the basis measurements
new
(Fig.
L= S for PhTlC12.NiPlEA2
References p_ 489
2
compounds
of IR and
L= 0 for PhT1C12.Nisalen
Fig.
of
a CSv point-group
of the thiocyanate
and the integrated
of >IeSTl
On the basis
in the latter
Another
in the solid
(9).
of these
I\'asassumed
(8).
compounds
[~le,X][(bIeST1)2F] from the reaction
of Djh symmetry
reported
respectively
organothallate
[?Ie4N]F in hot toluene
be assigned
system
to react l;ith E12NCX in l/l and
reported
to give Et2TlNMCN
[Me,X][kIe3T1CX] with
was
2).
470
These Italian authors also reported (12) that the l/l adduct formed from PhTICIZ
and
N,N'-ethylenebis(acetylacetoneimine)
dissociates into the parent components in methanol, as suggested by examining the IR, electronic
and
PMR
spectra
as well
as
the
conductivity. Bis(trimethylsilylmethyl)thallium (II, TlClS
x=
Cl;
or
III , X=
TlBr
Br)
(13).
have
been
Several
halides, prepared
other
(E-Ie3SiCHZ)ZTlX
from
hle3SiCH2Li
and
trimethylsilylmethyl
derivatives of Tl(II1) were synthesized starting from II as shown in Scheme 1.
Scheme 1 * TIOOCiPr RZTICl
RZTIOOCIPr
>
v
II I
1
Br2Py TIOOCiPr
[RTClBrl
Eg(OOCiPr)2
RT1(OOCiPr)2
>
VI JIeqSn I
1
TIOOCiPr
bIeRTlBr
MeqSn
MeRTlOOCiPr
7
VII
IV (R= Me3SiCH2)
Compounds
II,
III
and
in marked
contrast
to
This
has
Comparison
been
IV were the
attributed
found
polymeric to
the
to be dimeric in chloroform, dimethylthallium halides.
bulkiness
of
the
Me3SiCH2
group.
of the J(Tl-H) values in III and IV as well as in V,
VII and Me2TlOOCiPr suggested that the electronic effect of the Me3SiCH2 is very similar to that of the methyl
group.
That
VI
is
471
much
more
stable
or ethyl
analogs
toward
reductive
also was
decomposition
interpreted
in terms
than
its methyl
of the steric
effect. Mono-
and diarylthallium
di-t-butylphenol
VIII
stable
IX-XI
compounds
in polar
compounds
reacted
solvents
(14) as shown
to yield
with
2-amino-4,6-
diamagnetic,
in eq. 2-4.
(2) IX t 2
KHZ
OH
ArTl(OOCCF3)2
Ar,
,OTl
> Ar'
or Ar2TlOOCCFS
N
(3)
'OL X
(4)
I
-NH4X
Ar=
Ph, p-tolyl,
2,4,6-Me3C6H7,
E-C~C~H~ X= Cl, Br
On the basis
of the ESR measurements
PhT1(00CCF3)2
and VIII,
as
and XIII was
such
References
XII
p. 189
the existence suggested.
of the reaction of paramagnetic
mixture
from
intermediates
472
Ar,
Ar,
Tl
X
Tl
X'
X' H XII
XII and XIII chelate
Scheme
XIII
further
compounds
reacted
as shown
with
VIII
in Scheme
to form the eight-memberec
2.
2
VIII
f
XII
VII I
c
XI I H2 S
Tile IR and proton terms
of their Kumar
and Cc&,
et --
NF:R spectral
corresponding
data of IX-XI were
discussed
in
structure. al. extended
indenylthallium CgH7)
11
with
KX
the chemistry
derivatives.
Thus,
of cyclopentadienyl-
treatment
(X= CE, NCO, NCS, N3) afforded
organothallium
pseudohalides
(15).
of R2TlCl the IR studies
(R=
413
.indicated species,
these R2TlH
compounds (R= C5H5,
(16) from the reaction with
NaH
in THF.
2200
cm-'
potassium
values
salt
formed
atoms
C8H8TlCl
reported.
in THF
resulted
+
was
reaction
methane
of
in the presence
trienylthallium The
(C5H6N)2T1C15
in the formation
identified
compounds
with
of C8H8TlCl
states
+
NaCl
l
C7H7T1C12
with
the
in which
(eq. 5).
(Z= NMe,
in dichlorocyclohepta-
NC6H40Me-2,
or aldimines
as shown
in eq. 6.
The presence
of the quinonoid
solution
was
shown by the electronic
(5)
(18).
the aldehyde
with
0) were.-
Et2T10H tautomer
(19) in
spectra.
CH=Z OTlEt *
References p. 489
of the
'10H8
afforded
by boiling
structural
chloride
as (C8H8)2T12,
prepared
The
reported
W&$WIl,
cycloheptatriene
o-Et2T10C6H4CH=Z
CH=Z OH
and
THF ______3
of triethylamine
dichloride,
also
thallium(III)
thallium(I),
l/2 (C8H81 2T12
The
authors
are in +3 and +l oxidation
NaC10H8
to be prepared
or that of R2TlCl
These
by the reduction
of naphthalene
two thallium
Et3N
hydride
of 2105 cm -' for R= C5H5
of cyclooctatetraene
the product
sodium
with
claimed
of cyclooctatetraene
metal
salt
Ofganothallium
has been
of R2T1BH4
v(Tl-H)
reduction
potassium
while
C9H7)
for R= C9H7 were
(17) that with
to be ionic.
Et2T10H/
study
of diethylthallium
2,-----
salts
(6)
of polynitroalkanes,
474
CH (Mc12) 3,
thallium
CH2(NO2), iodides
electrolyzing
R,TlI i
of K2HP04
separated
with
Various
using
a ceramic
thallation
methyl
method,
diaphragram
trimethylsilanes
as in eq.
FIe3SiC6114S
+
synthesized
3-Cl,
3-Br,
also
found
to react
FIe3SiOOCCF3
and CF3COO?fe, probably
report
The proton
(Tetrahedron
above
XYR data
were
(22) using
(23) that
be isolated
Letters,
?!e3SiOOCCF
x-
the formation
(71
3
2-F, 2-Cl,
acid
work,
of
for the arylthallium A reexamination
and Tl(OAc)3 adduct
does exist
of the
on the reaction
of
now has
XIV, which
could
not
as a well-
material.
T~(OAC)~ ------+
COOH
aryl-
with Ye Si to form 4
(1966) 1363)
the oxythallated
in the former
characterizable
+
3-CF 3, 3-(Me,
reported.
S-norbornene-2-endo-carboxylic confirmed
reported
4-CF 3, 4-Ph
was
obtained
some of which
CF+OOI! p-_-3
Tl(OOCCF3)3
Tl(OOCCF3)3
compounds
in aqueous
7.
S= I!, 3-?Je, 3-F,
>leTl(OOCCF3)2.
by
(21).
SC61i4T1(OOCCF3),
2-Ne,
prepared
ahd a Pt-riire anode
by the previously
now been
Diorgano-
iodides
bistrifluoroacetates,
obtained
have
and ethyl
a Tl cathode
arylthallium
not be readily
(20).
reported
(R= CII2CH2CZi. Ffe, Et) were
B-cyanoethyl,
solutions
could
and ?!eCII(N02), was
(81 0
XIV
475
XV and XVI were
obtained
similarly
(eq. 9,lO).
(9)
4
Tl (OAc) COOH COOH
(Ac0)2Tl 3
@? 0 O
13 C MR reported
data
nuclei
for a series
by two groups.
and chemical
coworkers
(24).
chemical
that
withdrawing
on chemical detailed
In a related
shifts
description
NMR spectra
of the Tl(II1)
couplings
5.
was
Compounds
reported
these
electron-
(2.5), substituent were
derived
(26).
Containing4halliurrmetal study
Tl(1)
given.
tetramethyl
The
13C
ester
The pattern contact
of 13C-T1 mechanism.
Bonds
on the stability
of both
was
a
of alkyl
shol+n.
of the Fermi
effects
after
assignment
group was
coproporphyrin
in terms
authors
on alkyl-substituted
of signal
and assigned
interpreted
derivatives
References p_ 489
derivatives, is a powerful
and
Kitching
and "F
constants
to the Tl(OOCCF,),
A comparative carbonyl
by
of 6J(13C-205 Tl) on the conformation
para
were
of coupled
the 13C data
study
of the method
were
205 Tl couplings
discussed
by Ernst
and coupling
side-chains
chelates
group
trifluoroacetates
The dependence
were
of the p-fluorophenyl
group.
arylthallium
of 13C_203,
of both
the T1(00CCF3)2
compounds
on the disposition
effects
On the basis
shifts
suggested
shift
XVI
of arylthallium
The range
the dependence
to be expected,
(IO)
COOH
F
of transition-metal
and Ti(II1)
was
reported
(27).
476
Tl[Co(C0)4] Scheme
3.
Scheme
3
Tl+
XVII was prepared
rcowx41,q
+
aq
by several
methods
as shown
in
Hg [Co (CO) 412
.
Y Tl
The new
compounds
W) have
been
with
T1N03
synthesized
or T12S04
and Tl[Mn(CO)3] where
nation
in water.
reactions
The existence
inferred
of the
+
by examining
latter
stability
4HMn(C0)3
of these
(eq. 12) was
M(C0)3Cp
M= Cr; XIX, M= MO, XX, FI=
was
of Na[M(CO)3Cp
of T1[Co(C0)3PPh3] the IR spectra
accomplished
through
the
reaction.
[Tl(OEt)]4
The
(XVIII,
by metathetical
has been
the formation
following
found
.->
Tl(1)
4Tl[Mn(C0)3]
compounds
to decrease
toward
in the order
+
4EtOH
(11)
disproportioX= COG>
(W>Mo>Cr)>Co(C0)3PPh3=Mn(CO)5~Fe(CO)2Cp.
3TlX
The
T1[M(C0)3Cp]
KOI41 3
Tl[Co
W
TlX3
corresponding
to undergo
T1X3
a reversible
a greate.r or lesser and the stability particularly
+
2Tl
compounds reductive
degree
(12)
were
characterized,
elimination
depending
on the reaction
of the TlX compounds,
promoted
by light.
process
and found (eq.13) conditions
such elimination
being
to
477
c-
TlX3
TlX
The reversibility
+
of this
Tl[Co(CO)4],[W(CO),Cp] CO2(CO)8.
Closely
stability
of Tl(1)
function
the pK,
,I,
PQ-0C6H4Cl) the reaction of pKa>5
of XVII
to eq. 12.
Behrens
XXII,
M= MO)
SnPh3),
shown
Similarly
SbPh3,
obtained
T1[Fe(C0)3NO]
anions,
X-
and from
give HCO(CO)~L
but T~[CO(CO)~L]~ PnBu3)
were
resulted
Tl[Fe(C0)4R]
[M(CO)~CP]~
(R=
In related
T1[M(C0)3Cp]3
and
to be a
obtained
and T1[V(C0)6].
obtained metal
were
L which
derivatives
AsPh3,
thallium
was
the
5 (L= P(OPh)3
T~[CO(CO)~L]
the Tl(1)
and coworkers from
carbonyls
those
and
(28) in which
is less than
and L, while
P(OEt)3,
complex
of such metal-carbonyl
compounds
form
according
work,
strength
the mixed
from T1[W(C0)3Cp]
appeared
of HCo(CO)3L
P(OMe)3,
COPh,
work
transition-metal
(L= PPh3,
CH2CN,
enabled
to be prepared
stable
did not
(13)
reaction
related
of the base
when
Thus,
X-X
(XXI, El= Cr; (29)
(eq. 14).
0
3PfCCO13CP12
+
2Tl
&
2T1[M(CO)3Cp]3
(14)
THF M= Cr, MO
The reaction XVIII
reacted
Treatment Addition
of
[Cr(C0)3Cp]2
with
of XVIII of iodine
solid with
with
KBr
excess
to give K[Cr(C0)3Cp]
[Cr(CO),Cp],
to XVIII
thallium
afforded
and TlBr.
gave XXI according
also afforded
XXI
XVIII.
to eq. 13.
(eq. 15).
0
3T1[Cr(C0)3Cp]
+
12-_,
T1[Cr(C0)3Cp]3
+
2TlI
THF Structure studied References
in sqme p. 489
and some detail
reactivities by Schussler
of T~[CO(CO)~] et al ---
(38).
XVII were The X-ray
(15)
478 crystal ionic
structural
solid
discrete
determination
composed
close
are consistent
with
solvents
of high
abilit)- (water, Co(CO),,
while
moieties
DXSO,
ability
the presence
of tight
of covalent
to react
with
crystalline
Tl[Co(CO)4]
The reactions
which
were formed
InBrS),
CoC12.
The
study
was
extended
was
synthesized
from
with
lithium
VT1
The reaction
of this
compound
halides
Unlike
significant
to afford
found
very
(eq. 16).
the other
metal
f
with
IIIb
X-Y3 compounds
of type ?1C02Brj(Co)6
the cobalt
LIIb metal-tin (32).
(161
of the Group
or clusters
and Oliver
4FIejT1
the formation
in CHzC12
with
XVII was
observed.
chlorinated
on the Group
+
allowed
were
and rieak
WCoCW,12
(31).
merely
by Keibel
In
into Tl+ and
consistent
ions with
in solution
(BXS, AlXS)
TlClS
bonds.
constant
IR spectra
(
of Co2(CO)8
adducts
which
[(PhCU2)Ph3P]{Tl[Co(Co)517j
Co(W);
investigated
(GaBrS,
3Li
bonding
atoms
dissociates
or triple
dissociated
*
nor are there
covalent
of lox dielectric
ion-pairs
Tl-Co
is extensively
metals
D?.!F),the compound
(TflF, CH,C12),
are no
and good coordinating
[(PhCHZ)Ph3P][Co(C0)41
air-sensitive which
of strong
constant
in solvents
state,
betrceen Tl and other
the existence
dielectric
is an essential
There
ions.
in the solid
distances
coordinating
amounts
that XVII
of Tl+ and Co(CO),
Tl[Co(C0)4]
any particular
showed
carbonyl
bonded
to
compounds
In this work,
Li[Tl?le4]
and FieSTl (eq. 17).
3Li[Tl!Ie4]
varying
amounts
of Li[T1(>le3Sn)nFle4_n]
(17)
of Me6Sn2
(n= l-4)
(eq. 18).
479
Li[TIFleq]
+
nNegSnq
>
Li[T1(NegSn)nEle4_n]
SIR
Proton
analogous The 3
for
factors shifts
4.
in the
vas
were
of
compounds Ga,
afforded
of
(C6FS)2T1S
SAu(CoFS),L with
resulted
in no
tion was
observed.
of
TlS
for
reported.
'J(Sn-II),
'J(Tl-II)
of both _‘Iand n.
and
The
and the chemical
Br,
I) with
Ph,
A possible
Analogous SOS,
intermediate
x;as postulated
as
shown
SAUL
reactions
O&z,
but
'(L= PPhS,
SCM,
PPh3+)
substitu-
ligand
for the reactions
belot;.
CoF5
also
reacted
(34).
The
the interaction
In this study
EtZIIg7 was
probably
(eq. 19).
\ C6F5-Tl-X // fr-Au
or
with
PtC1Z(PEt3)z
PtCl,(PEt3)iTl(C6F5)2Br
respectively
ion
(18)
been
.&I(I) to Au(II1)
C6F5-T&-S-Au-L / Br
surface,
have
(35).
(Y= C6FS,
'gF5,
to study
Sn
Compounds (S=
and
Y‘AuPPhS
oxidation
S= halogen
to afford
4
as xiell as
in the couplings
Organothallium(I11)
reactions
(C6F5)?T1Br
In)
'J(Sn-H),
as a function
the changes
of
(C6FS),T1Br
with
(!-!=Al,
nNe
proposed.
Reactions
AsPhS)
tallium-tin
values
discussed
governing
The
such
Li[?I(!4e3Sn)>~e3]
variation
J(Tl-II)
of
data
+
or PtCl(C6F5)(PEt3),.Tl(CgFg)ZBr,
galvanostatic of Et2T1* shown
or PtC1(C6F5)(PEt3)2
method
ion with
to be formed
via the formation
has been mercury
employed
metal
(35).
on the mercury
of an intermediate
[EtHgTIEtlC
480 Hg Et2Tl+
The
+
Hg e[EtHgTlEt]+
formation
Ph2Tl(NCS)i-" distribution A 25 anion Ph2TlNCS
constants
exchanger
determined
of PhT12*
and aqueous
-for n= l-4, respectively,
were
at 25' from
and Ph2TlC
log B,= 2.3,
obtained;
Me2T10H
OH- catalyzed at 25O, it was
constant
exist
in aqueous
The reaction (n= O-3), which
characterized.
has been adducts
XXIV
by Me3SiNj
and Me3SiNC0,
X
20-22.
from
conditions
studies alcohol
constant
of the by
(dissociatio 1.5 M-l>
(37).
(38).
were
further
T~(OAC)~_~(N~)~
varying
investigated
isolated converted
amounts
of
With and to XXVI
and
respectively.
XXIII
X=Y=Z=N3
XXIV
X=Y=Z=OAc
xxv
X=N3,
XXVI
X=Y=OAc,
XXVII
X=N3,
such oxythallated affording
or
3.9, 4.7 and 4.8
ion pairs
by mixing
XXIII-XXV
Sephadex
PhTl(NCS)2
From
the system
and XXV were
(-JQTIYZ
several
with
can be generated
and Me3SiN3,
Dethallation
that both
solution
the
between
of diacetone
(dimerization
of olefins
benzonorbornadiene,
XXVII
concluded
0.090 M) and dimers
of Me2TlOH
Tl(OAc)3
decomposition
and
for Ph2T1(NCS)n1-n,
log B,= 0.1 and 0.6 for n= 1,2 respectively. specific
(19
Et2Hg2
(n= l-4)
KSCN containing
For PhT1(NCS):-n,
(36).
+
Tl
of PhTl(NCS)i-"
(n= 1, 2) were coefficients
+
C
various
adducts
Y=Z=OAc Z=N3
Y=OAc,
Z=NCO
was performed
compounds
as shown
under in eq.
481
N3
HX XXIII
or XXV
6
(x= F, Cl,
X
(20)
I, OH)
& -Tl(I) XXVI
A
XXVII
u
(21)
&:3 -Tl(I)
The
reaction
proceeded
(22)
of T1(OAc)3/Me3SiN3
according
with
to eq. 23 and
norbornene
or norbornadiene
24.
3
Tl(OAc) 3/Me3SiN3
HX/H20 \
A full account
>
of the study by Uemura
thallation
of acetylenes
appeared
acetylenes
$th
in acetic
acetoxythallated
T~(OAC)~ products
-et al. on the acetoxy-
Treatment
(39).
acid yielded
of alkylphenyl-
two isomeric
trans-
(eq. 25).
Tl(OAc)3 PhCZCR
> T~(OAC)~
Ph 'C-C' AcO/
'R
References
p- 489
Ph,
OAc c=c/
(AcO)~T~'
nB~
(25) 'R
XXIX
XXVIII R= Me, Et, "Pr,
+
482 Heating of
XXVIII
and XXIX
PhC(OAc)=CHR
The same
in acetic
and PhCH=C(OAc)R
compounds
hydrogenolysis
also were
of XXVIII
showed
the hydrogen
from
sequence
Scheme
the solvent, (Scheme
deuterium
group
the following
4).
,Tl(OAc)2
BH;
Ph,
c=c ’
f
experiments
suggesting
7'
AcO /
solvents
of the Tl(OAc)2
4
Ph,
from
in protic
labelling
from NaBH4,
3
Me
_ c-c
BH3 ‘=-0
,Tl\
&Me
ROH
H
Ph
> -HTl(OAc)
2
-
0' 'Me
AcO/
'CZC' AcO'
'Me
-BH3(0R)
Treating
XXVIII
with
CuX or CuX2
CN, SCN) with
retention
prepared
oxythallated
some
and investigated adducts
reacted
the corresponding good yields
adducts
the reactivities with
copper(I)
alkyl
gave PhC(OAc)=CRX
of configuration.
halides
These
of styrene of these
halides
(X= Cl, Br, authors
I,
also
and a-methylstyrene
adducts
(40).
and pseudohalides
and pseudohalides
The to affor
in moderate
to
(eq. 26, 27). T1(OOCRz)3 >
PhCRl=CH2
PhCR1(OR3)CH2Tl(OOCR2)2
(26
R30H
RI=
H, Me; R2= Me, iPr, nBu,
iBu
;
of configuration.;
products
NaBH4
for replacement
not
in the formation
retention
and XXIX with
In this reaction,
came
with
the principal
at pH 6-7. that
acid resulted
iPr; R3= Me, Et, nPr
483
PhCH(OR
cux
.3 )CH2Tl(OAc)2
B
PhCH(OR3)CH2X
(27)
X= Cl, Br, I, CN, SCN; R3= Me, Et, "Pr,
The effects KX were
of both
examined.
the nature A possible
halogenodethallation
The kinetics
in H2O/MeOH
Analysis
dissociates
of the oxythal,lated
PhCH(OMe)CH2Tl(OAc)2
The products
and its dimethylacetal. law.
proposed
The
for such
species
were
follows
parameters
adduct
XXX has been
identified
reaction
of the kinetic
into a reactive
of
is
of decomposition
(41).
and the addition
intermediate
reaction
and styrene,
Tl(OAc)3
of solvents
nBu
studied
phenylacetaldehyde
a first
indicated
RTlOH+
from
order
rate
that XXX
and a more
reactive
RT12+- (eq. 28).
RT~(OAC)~~
RTlOAc+
+ OAc-
cH2°
H+ RTlOH+e
RT?
(28)
R= PhCH(OMe)CH2
The
implication
determining largely The Tl(N03)3
References
step
depends
of this
is that
in the overall on experimental
distribution
of products
of the olefins
p. 489
study
RCH=CH2
the nature
oxidation
of the rate-
of styrene
by Tl(II1)
conditions. formed
in the oxidation
and R1R2C=CH2
in methanol
by has
484 been
studied
from
the former
formed.
(42).
With
olefins-
RIRZC=CH
the formation
log kl/k,= result
better
was
2-butene has
diols,
Taft
was
the
$
for
t 2:
R1COCH2R
;
by the equation,
that
the migration
of the
A possible
reaction,
preferentially.
and its dethallation
study
by Bertsch
and _cis- and trans-stilbene
but mono-
of
-!
p*= -4.
of the oxidation
the formation
formed
constants
that
constants
were
diether
the
of the rate
to suggest
In a related
only
(kl) versus
with
occurs
and RCOMe
CHZCl
RlR2C(OMe)CH2T1X2
examination
confirmed
compounds
~*(a~*-al*)
donor
R=
the ratio
to the polar
involving
discussed.
a careful
2'
led the authors
electron
sequence
When
of the RZCoCHZR1
(k2) was related
This
Both RCH(OMe)CH2OMe
with
of not only
and dinitrate
T1(N03)3
(43),:
2,3-dimethylin methanol
the carbonyl
esters
step
and Ouellette
of I-decene,
and dimethoxy
of the corresponding
e.g. _-
Tl(NO3)3 Me2C=CMe2
> MeOH,
2 Me3CCMe
+
Me2C -CMe2 I I OMe Oble
O0
(45%)
(3%) c
Me 2C -
CMe
I2
I
+
ONe 0N02
Me2C I ON02
(34%)
Stereochemical
analyses
stilbene
led the authors
proceeds
in a trans
of the products to
fashion,
believe e.g.
that
CMe
2
I
(291
ON02
(18%)
from
cis-
and trans-
the initial
in Scheme
5.
1
oxythallation
466
Optical
Jcemic
i3;:3
cl7
Product
TlX,
L-I!
R= AC, iIe, Et
OR X= Ok,
SOS
(S)-XXX11
OR
(S)-XSSIII methoxy-
Similarly, gave
optically
and ethokythallation-dethallation
active
facts
led the authors
XXXIV
cannot
purity
In other
wcrk
noradamantane XXXV
process
Scheme
to suggest
involves
of XXX111
XXXVI,
XXX111
that
to XXX11
an anti mode
which
to give
was
had been
a 60% yield
The
of addition.
with
prepared
cation
and that the
reduced
treated
allylic
when
S= NOS.
Z-methylene-
from Z-noradamantanon
of 4-protoadamantanone
7). ,Ok
7 Ol%
D1, D=rLl
\__
also
These
(R= Me, Et].
the planar
(R= Me, Et) was
(451, Tl(ClO,)S
and PhSPCH,,
(Scheme
ethers
be the sole precursor
oxythallation optical
allylic
of XXX1
TV rr,n , XzTlCH&
XSXVII'
487 0
-Tl(I)
423 XXX\-1I
The
formation
of XXSVII
intermediate position
involving
resulting
and a subsequent the fact that is treated different
was
assumed
to be a consequence
a cationoidic
methylene
from the exo attack These
dethallation.
the isomer
of SXXVII
tcith diazomethane conformation
in an axial
of II,0 L in osythallation sequences
is formed
in ?IeOH owing
bearing
group
of an
l
selectively
with
when
XXXV
to an intermediate
an exo cationoidic
methylene
of as in
eq. 30.
XXXV
CH,N:, - -> bleOU
study
A comparative Tl(III)
and Pb(iV)
products RCONe,
identified
from the Tl(III)
(R= C6HI3).
impurity
discussed
of decomposition Some organic
other
effective
studies
Tl(ClO4)3
in the presence
importance
of chalcones
(48), iodination of Tl(OOCCF3)3
include
came
distribution
of several
ways
adducts.
the synthesis
of g-quinols
The
and
compound
The product
oxidant.
of the application
rearrangement
oxidations i
in the last
by Hg[II),
(46).
RCH(OAc) CH_,OMe
of the relative
include
synthesis
in-methanol
and Pb(IV)
of the oxymetallated
synthesis
the oxidative
Chlorine
in the metal
in terms
of the oxidation
of 1-octene
i.
from Cl-
with
acetates
made
RCH(011e)CH20~!e, RCH(O\iejCH,OAc,
RCH(O>Ie)CHZCl
was
has been
of Tl(III)
compounds
of isoflavonoids with
by oxidation of benzene
Tl(xO3)3
to
through (47), an
of.E-alkylphenols
and mesitylene
(493, and iodination
with
by KI of
I2
488 arylthallium aromatic
bistrifluoroacetates
acids
Thallium(I)
derived
from Tl(OOCCF313
and
(SO).
Compounds
m- and p-Fluorophenylcyclopentadienylthallium(I) synthesized
19
and
F NMR
spectra
were
measured
in THF
have
been
(51).
The
chemical
shifts
were
compared
with
(M= alkali
metal) bond
and CL and o" values calculated thereof I R the respective values for MC3HqC6H4F-~(~)
and C5H3FeC3H4C6H4F-m(p).
ionicity
thallium(I)
has been
salt
previously
Commun.,
several
(1972)
TlOOCR/I2
the reaction
and coworkers
system
TlOOCR
and
yield
T12C2B9Hll
1178) has been (52).
was
obtained
utilized
for
the reaction
Thus,
with
Me2AsBr
extended
in organic 12 gave
their
synthesis.
study
of
in a 2/l ratio
the corresponding
+
TlOOCR
f
I2 v
(R= Me, CF3,
reactions
are regiospecific
of the products, A possible
of the use of treatment
Thus,
of alkenes
c-iodocarboxylates
::-c: I
iodonium
which
The
(53, 54).
3c=c;:
The
in THF.
(Me2As)2C2B9H11.
Cambie
._in high
to be 40-50%
arsacarboranes
3-R-3-As-1,2-C2B9Hll;
with
thallium-cyclopentadienyl
with RAsX2 (R= Me, X= Br; R= Ph, nBu, X= Cl) produced
T12C2BgHll
afforded
estimated
of 7,8-C2B9Hl12-,
(Chem.
synthesizing
The
offer
mechanism ion type
intermediate
AOCR
Ph)
and in conjunction
an alternative
involving
(31)
with
to the Prevost
an iodine-alkene and a Tl(1)
solvolysis
reaction.
s-complex,
species
rather
an than
a
489
Tl(III)-olefin
interaction
has been
of unsaturated
thallium(I)
carboxylates
IZ gave
a convenient
conditions
to the Survey
Solutions
various
reaction
e.g.T100C(CH2)nG=C( --
for iodolactonizatibn
with
under
neutral
(55).
Complementary
prepared
procedure
A similar
discussed.
Covering
of the 5-bromo-
by treatment solvents
These
to the unsubstituted
1973
or 5-chlorocyclopentadienes
of CpTl with
(56).
the Year
were
the N-halosuccinimide
5-halocyclopentadienes
cyclopentadienyl
cation
in
were
on treatment
converted with
SbF5.
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