Synthesis and characterization of FvW2(CO)4L2(SR)2 (L=CO, PPh2Me; R=H, i-Pr, CH2Ph, Ph) type (fulvalene)tungsten dihydrosulfides and dithiolates

Article abstract of DOI:10.1016/S0022-328X(99)00158-8

A direct, high-yield synthesis of (Et₄N)₂[FvW₂(CO)₆], where Fv=η⁵:η⁵-C₁₀H₈ (fulvalene), from W(CO)₃(EtCN)₃, Li₂[C₁₀H₈], and Et₄NBr is reported. It reacted with sulfur-transfer reagents, RSphthalimide (R=i-Pr, CH₂Ph, Ph), to give the corresponding dithiolato complexes, FvW₂(CO)₆(SR)₂. Treating the thiolato complexes, where R=i-Pr, CH₂Ph, with CS₂ gave thioxanthate derivatives FvW₂(CO)₄(S₂CSR)₂, via mixed RSW(CO)₃(μ-Fv)(CO)₂WS₂CSR intermediates. The unstable bishydrosulfido complex FvW₂(CO)₆(SH)₂ was obtained from FvW₂(CO)₆H₂ and S₈ via the mixed hydrido-hydrosulfido intermediate FvW₂(CO)₆(SH)H. FvW₂(CO)₆H₂ also reacted with PPh₂Me to give the ligand-substituted product FvW₂(CO)₄(PPh₂Me)₂H₂, which provided access to the dianion Li₂[FvW₂(CO)₄(PPh₂Me)₂] via methyllithium reduction. Similarly to its parent compound, [FvW₂(CO)₄(PPh₂Me)₂]^2- also gave the corresponding dithiolato complexes, FvW₂(CO)₄(PPh₂Me)₂(SR)₂ (R=i-Pr, CH₂Ph, Ph), upon treatment with RSphthalimide. FvW₂(CO)₄(PPh₂Me)₂(SPh)₂ was converted into FvW₂(CO)₄(PPh₂Me)₂(SH)₂ under an atmosphere of H₂S. All PPh₂Me-substituted dithiolato complexes as well as the bishydrosulfide derivative exist in solution as an equilibrium mixture of D,L- and meso-cis,cis, cis,trans and trans,trans isomers. However, only the cis,cis isomer of the bishydrosulfido complex was present in the crystalline state.

Full text of DOI:10.1016/S0022-328X(99)00158-8

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 586 (1999) 31–40
Synthesis and characterization of FvW2(CO)4L2(SR)2 (L=CO,
PPh2Me; R=H, i-Pr, CH2Ph, Ph) type (fulvalene)tungsten
dihydrosulfides and dithiolates
Istva´n Kova´cs, Alan Shaver *
Department of Chemistry, McGill Uni6ersity, 801 Sherbrooke Street West, Montreal, Que´bec H3A 2K6, Canada
Received in revised form 24 February 1999
Dedicated to: Professor La´szlo´ Marko´ on the occasion of his 70th birthday.
Abstract
A direct, high-yield synthesis of (Et4N)2[FvW2(CO)6], where Fv=h5:h5-C10H8 (fulvalene), from W(CO)3(EtCN)3, Li2[C10H8],
and Et4NBr is reported. It reacted with sulfur-transfer reagents, RSphthalimide (R=i-Pr, CH2Ph, Ph), to give the corresponding
dithiolato complexes, FvW2(CO)6(SR)2. Treating the thiolato complexes, where R=i-Pr, CH2Ph, with CS2 gave thioxanthate
derivatives FvW2(CO)4(S2CSR)2, via mixed RSW(CO)3(m-Fv)(CO)2WS2CSR intermediates. The unstable bishydrosulfido complex
FvW2(CO)6(SH)2 was obtained from FvW2(CO)6H2 and S8 via the mixed hydrido–hydrosulfido intermediate FvW2(CO)6(SH)H.
FvW2(CO)6H2 also reacted with PPh2Me to give the ligand-substituted product FvW2(CO)4(PPh2Me)2H2, which provided access
to the dianion Li2[FvW2(CO)4(PPh2Me)2] via methyllithium reduction. Similarly to its parent compound,
[FvW2(CO)4(PPh2Me)2]2− also gave the corresponding dithiolato complexes, FvW2(CO)4(PPh2Me)2(SR)2 (R=i-Pr, CH2Ph, Ph),
upon treatment with RSphthalimide. FvW2(CO)4(PPh2Me)2(SPh)2 was converted into FvW2(CO)4(PPh2Me)2(SH)2 under an
atmosphere of H2S. All PPh2Me-substituted dithiolato complexes as well as the bishydrosulfide derivative exist in solution as an
equilibrium mixture of D,L- and meso-cis,cis, cis,trans and trans,trans isomers. However, only the cis,cis isomer of the
bishydrosulfido complex was present in the crystalline state. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Fulvalene; Tungsten; Thiolate; Hydrosulfide; Carbonyl; Phosphine; Substitution; Thioxanthate; Isomerism
and S8 as in the Claus reaction. Complexes I and II are
the first homogeneous catalysts of Claus chemistry [1a].
1. Introduction
These observations prompted a search for other
bishydrosulfido and dithiolato complexes which might
been successfully applied in recent years for modeling
Well-defined, soluble transition metal complexes have
plausible surface reactions of the heterogenous Claus
process [1]. Most notably, it was found that cis-
(PPh3)2Pt(SH)2 (I) (Scheme 1), which was selected as a
model of preabsorbed H2S on the catalyst surface,
reacted with SO2 to give (PPh3)2PtS3O (II) and H2O.
Complex II, in turn, afforded a mixture of I, H2O, and
S8 under an atmosphere of H2S, completing a catalytic
cycle in which SO2 and H2S were converted into H2O
* Corresponding author. Tel.: +1-514-3986999; fax: +1-514-
3983797.
Scheme 1.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00158-8

32
I. Ko6a´cs, A. Sha6er / Journal of Organometallic Chemistry 586 (1999) 31–40
be suitable models for studying the reactions of acti-
vated H2S with SO2 and, ultimately, catalysts of the
Claus process in homogeneous phase. Dinuclear (fulva-
lene)tungsten complexes of the type FvW2(CO)4L2(SR)2
(III) (Fv=h5:h5-C10H8; R=H, alkyl, aryl; L=CO,
phosphine) appeared to be particularly interesting.
sulfide or thiolate functions is outlined in Scheme 2. This
required [FvW2(CO)6]2− as the starting material in
relatively large amounts and thus, a convenient and
efficient preparative method was sought. [FvW2(CO)6]2−
has been prepared recently by the sodium-amalgam
reduction of FvW2(CO)6(W–W) [7c], but the practical
scale synthesis of the latter has a considerable disadvan-
tage in that it requires careful purification of extremely
unstable dihydrofulvalene [7e]. Therefore, we established
the direct synthesis of (Et4N)2[FvW2(CO)6] (1) by adopt-
ing a procedure successfully applied previously for the
preparation of its molybdenum [8g] and chromium [9a]
congeners. Complex 1 was obtained in practically quan-
titative yield as a mixture with NaI and LiBr, indifferent
side-products of the synthesis of Li2[C10H8] and the ion
exchange with Et4NBr, respectively, which sponta-
neously separated in subsequent reactions due to insolu-
bility (Eq. (1)). Complex 1 was identified by its
spectroscopic properties [7c].
On one hand, fulvalene systems have already been
under scrutiny as models for the interactions of organic
molecules with metal surfaces [2]. The metal centers
anchored to and held in close proximity by the fulva-
lene ligand such as complex III can be considered as
two neighboring active sites on a catalyst surface. On
the other hand, the chemistry of analogous (cyclopenta-
dienyl)tungsten carbonyl hydrosulfides [3] and thiolates
[4], Cp(CO)2(L)WSR (R=H, alkyl, aryl; L=CO,
PPh3, CNR%), has been relatively well developed and
provide a reliable starting point for the synthesis of the
target fulvalene derivatives. In addition, since steric and
electronic interactions between the two halves of fulva-
lene complexes through the bridging p-system often
generate reactivity patterns different from those of the
corresponding mononuclear cyclopentadienyl ana-
logues, they could easily be used for comparison.
Here we report the synthesis, characterization, and
some reactions of the (fulvalene)tungsten complexes
FvW2(CO)4L2(SR)2 (L=CO, PPh2Me; R=H, i-Pr,
CH2Ph, Ph). To our knowledge, only two (fulva-
lene)metal thiolates, Fv[CpZr(SPh)2]2 and Fv[CpZr(m-
SPh)]2, have been reported to date [5a]. These
complexes and the sulfide-bridged complexes
Fv[CpTi(m-S)]2 [5b] and Fv[CpZr(m-S)]2 [5a] represent
the known sulfur chemistry of fulvalene compounds,
which therefore remains practically unexplored. Fur-
thermore, dinuclear complexes containing nonbridging
hydrosulfide or thiolate groups in general are rare [6],
probably owing to the strong Lewis-basicity of sulfur.
Thus, it is surprising that the title complexes showed no
sign of bridge formation. Note that this work also
contributes to the relatively unexplored chemistry of
(fulvalene)tungsten carbonyl complexes in general [7],
compared to that of molybdenum [8] and chromium
derivatives [8i,9].
2W(CO)3(EtCN)3+Li2[C10H8]+2Et4NBr
“(Et4N)2[FvW2(CO)6]+2LiBr+3EtCN
(1)
Complex 1 was protonated by glacial acetic acid in
toluene to give FvW2(CO)6H2 (2), which was either
isolated by crystallization or utilized in situ. Complex 2
was identified by its spectroscopic properties [7c]. Since
we were also interested in phosphine-substituted thiolato
and hydrosulfido complexes as dinuclear analogues of
CpW(CO)2(PPh3)SR (R=H, i-Pr, Ph, CH2Ph) [4c,d],
complex 2 appeared to be a potential candidate to
introduce a relatively large phosphine. Although com-
plex 2 reportedly failed to react with PPh3 [7c], we found
that ligand substitution proceeded smoothly with
PPh2Me at elevated temperatures to give the new dihy-
dride FvW2(CO)4(PPh2Me)2H2 (3) in good yield.
The identity of complex 3 was confirmed by IR (Table
1) and NMR spectroscopy, combustion analysis, and
indirectly, by converting it into the known diiodide
FvW2(CO)4(PPh2Me)2I2 [7a] by hydrogen–halogen ex-
change with CHI3. The 1H-NMR spectrum of 3, recorded
in acetone-d6 at room temperature (r.t.), exhibited an
asymmetric doublet at l −7.08 (JP–H=55 Hz) with
183W satellites (JW–H=48 Hz) which was assigned to
hydridic protons. A well-resolved doublet characteristic
of the PMe group appeared at l 2.22 (JP–H=8.6 Hz) and
additional broad resonances were observed in the down-
field region consistent with the presence of fulvalene and
phenyl groups. In the 13C{1H}-NMR spectrum, two
fulvalene (l 86.3 and 87.6) and three phenyl resonances
could be identified, but no quaternary and PMe carbon
resonances were detected. The 31P{1H}-NMR spectrum
exhibited a broad signal at l 19.3. All these features are
fully consistent with the composition of complex 3 and
the fact that its four possible isomers: meso-cis,cis,
D,L-cis,cis, cis,trans and trans,trans are in a rapid equi-
2. Results and discussion
2.1. Synthesis and characterization of starting materials
and intermediates
The synthetic pathway designed to gain access to the
title (fulvalene)tungsten complexes containing hydro-

I. Ko6a´cs, A. Sha6er / Journal of Organometallic Chemistry 586 (1999) 31–40
33
Scheme 2. (i) RSphth (R=iPr, CH2Ph, Ph), THF, r.t. (ii) excess AcOH, toluene, r.t. (iii) S8, THF, r.t. (iv) PPh2Me, toluene, 110°C (P=PPh2Me).
(v) MeLi, THF, −10°C. (vi) CHI3, toluene, r.t. (vii) RSphth (R=iPr, CH2Ph, Ph), THF, r.t. (viii) excess H2S, THF, r.t.
ing a symmetric molecule. Complex 4 readily afforded
complex 3 in the presence of a proton source and can
be easily oxidized to give the new metal–metal
bonded dimer FvW2(CO)4(PPh2Me)2(W–W). Owing
to its high reactivity, complex 4 was usually pre-
pared in situ from complex 3 in THF solutions and
used immediately for the synthesis of dithiolato com-
plexes.
librium on the NMR time scale under ambient condi-
tions (Scheme 3). This behavior has been well docu-
mented recently for FvW2(CO)4(PMe3)2H2 [7c] and
the analogous chromium [9a] and molybdenum [8g]
dihydrides by variable-temperature measurements.
Complex 3 was reduced by methyllithium to give
the dianion Li2[FvW2(CO)4(PPh2Me)2] (4), which was
isolated as a yellow solid. Its IR spectrum exhibited
two strong CO bands at 1663 and 1789 cm−1, consis-
tent with the high electron density on tungsten. Both
the 1H- and 13C{1H}-NMR spectra featured methyl,
phenyl, and fulvalene resonances, consistent with the
proposed structure. The 31P{1H}-NMR spectrum ex-
hibited a relatively low-field singlet at l 28.8 suggest-
2.2. Synthesis and characterization of dithiolato
complexes F6W2(CO)4L2(SR)2 (L=CO, PPh2Me;
R=i-Pr, CH2Ph, Ph)
It has been established that reactions of the anions

34
I. Ko6a´cs, A. Sha6er / Journal of Organometallic Chemistry 586 (1999) 31–40
Table 1
spectroscopy, the data being fully consistent with the
suggested structures.
Carbonyl stretching frequencies
The IR spectra of 5–7 exhibited two absorbances
in the regions 2017–2024 (s) and 1929–1939 (vs)
cm−1 consistent with the anticipated decrease in the
basicity of the thiolate group in the order of SiPr\
SCH2Ph\SPh. Common features of all 1H-NMR
spectra were two pseudotriplets attributed to Ha and
Hb protons of the fulvalene ligand. In addition, the
resonances for the SR groups indicated two such
equivalent groups in each complex. 13C{1H}-NMR
spectroscopic measurements supplemented the above
observations. The two low-field resonances of com-
plex 5, for instance, at l 214.1 and 226.5 which are
attributed to the cis and trans CO ligands, respec-
tively, are consistent with the presence of three CO
ligands about each metal center and with no ex-
change on the NMR time scale at r.t. The three ful-
valene resonances attributable to Ca and Cb and
bridgehead carbon atoms (l 91.3, 93.2, 108.1) again
support the proposed formulations.
Compound
w(CO) (cm−1 a
)
(Et4N)2[FvW2(CO)6] (1)
1892 (s), 1800 (vs),
1777 (sh), 1716 (m)
2018 (m), 1929 (vs)b
2017 (s), 1929 (vs)
1950 (vs), 1874 (m)
2018 (s), 1930 (vs)
2024 (s), 1939 (vs)
2023 (s), 1937 (vs)
1928 (vs), 1847 (s)
1949 (s), 1870 (vs)
1789 (s), 1663 (s)
1927 (m), 1845 (vs)
1927 (s), 1846 (vs)
1930 (s), 1852 (vs)
1944 (m), 1862 (vs)
1937 (vs), 1857 (s)
FvW2(CO)6H2 (2)
FvW2(CO)6(SiPr)2 (5)
FvW2(CO)4(S2CSiPr)2 (5B)
FvW2(CO)6(SCH2Ph)2 (6)
FvW2(CO)6(SPh)2 (7)
FvW2(CO)6(SH)2 (11)
FvW2(CO)4(PPh2Me)2H2 (3)
FvW2(CO)4(PPh2Me)2I2
Li2[FvW2(CO)4(PPh2Me)2] (4)
FvW2(CO)4(PPh2Me)2(W–W)
FvW2(CO)4(PPh2Me)2(SiPr)2 (8)
FvW2(CO)4(PPh2Me)2(SCH2Ph)2 (9)
FvW2(CO)4(PPh2Me)2(SPh)2 (10)
FvW2(CO)4(PPh2Me)2(SH)2 (12)
a Recorded in THF solution unless noted otherwise.
b In toluene solution.
The relative thermal instability of 5–7 suggested
that these complexes might have a versatile chemistry.
We have carried out spectroscopic investigations on
their reactions with CS2. CS2 readily inserts into the
[CpW(CO)2L]− (L=CO, PPh3) with N-alkyl-
(aryl)thiophthalimides (RSphth) give the correspond-
ing tungsten thiolate complexes, CpW(CO)2LSR
[4c,d]. We found that similar reactions took place
with complexes 1 and 4 leading to FvW2(CO)4L2(SR)2
(L=CO, R=i-Pr (5), CH2Ph (6), Ph (7); L=
PPh2Me, R=i-Pr (8), CH2Ph (9), Ph (10)). Com-
plexes 5–10 were isolated as poorly soluble,
orange–brown solids in moderate yields. While the
phosphine-substituted derivatives 8–10 proved to be
quite robust in solution even at elevated temperatures,
the parent carbonyls 5–7 decomposed to unidentified
product mixtures under similar conditions. Complexes
5–10 were characterized by IR (Table 1) and NMR
metal–SR
bond
of
CpW(CO)2(PPh3)SR
and
CpRu(PPh3)2SR to give the thioxanthate derivatives
CpW(CO)2S2CSR [4d] and CpRu(PPh3)S2CSR [10],
respectively. It appeared from these studies that the
insertion takes place via precoordination of CS2 to a
coordinatively unsaturated intermediate generated by
facile dissociation of PPh3. Similar reactions of Cp-
W(CO)3SR proceeded very slowly to also give Cp-
W(CO)2S2CSR [4d,o], consistent with the generally
slow CO dissociation from CpW(CO)3X type com-
plexes.
Monitoring the 1H-NMR spectrum of acetone-d6
solutions of 5–7 showed that 5 and 6 reacted quanti-
tatively at r.t. with a 10-fold excess of CS2 to give a
single final product in which both metal centers were
coordinated by a thioxanthate ligand. The reaction of
5 was complete in 3 days, that of 6 in 2 weeks, while
complex 7 did not react at all in 2 weeks. This obser-
vation points to a marked electronic influence on the
reaction rate. IR spectra suggested that one of the
three CO ligands per metal center were substituted in
the products (for instance, w(CO): 2017 (s), 1929 (vs)
for 5 versus 1950 (vs), 1874 (m) cm−1 for the
product (5B)) and the remaining two occupy mutually
cis positions, that is, a W(CO)2S2CSR system must
have been formed. The presence of equivalent CO
ligands in 5B, unlike in 5, was indicated by a single
13C-NMR resonance at l 243.2.
Scheme 3.
The formation of similar products in the reactions

I. Ko6a´cs, A. Sha6er / Journal of Organometallic Chemistry 586 (1999) 31–40
35
Scheme 4.
of analogous cyclopentadienyl and fulvalene tungsten
thiolates with CS2 suggests identical reaction mecha-
nisms, e.g. possible involvement of a 16-electron interme-
diate and precoordination of CS2 [4d]. However, the
fulvalene complexes appear to react faster with CS2 than
their Cp analogues [4d]. On the other hand, the reactions
of 5 and 6 proceed via the formation of monothioxan-
thate intermediates (5A, 6A) (Scheme 4), identified by the
observation of four fulvalene pseudotriplets and two
different CHMe2 methyl doublets or CH2Ph methylene
singlets of equal intensity in the NMR spectra. These
species were the only products in the early stages of
reactions and gradually disappeared concomitant with
the formation of the bisthioxanthate complexes 5B and
6B.
protons of the SCH2Ph ligand in cis isomers, similar to
the fulvalene protons. The PMe, methylene, and fulva-
lene proton resonances of complex 9 are shown in Fig.
1. The methyl doublets exhibit characteristic coupling to
phosphorus (JP–H=8.6 Hz) and were used to determine
the exact ratio of individual isomers. The resonances
attributable to cis isomers often appear upfield from
those of trans isomers [7c,9a]. The seemingly complex
multiplet of methylene protons is mainly due to the
cis,trans isomer which combines features of both the
‘pure’ cis,cis and trans,trans forms. In general, the
proton resonances of a methylene group attached to a
phosphine-substituted chiral metal center appear as an
eight-line ABX system due to coupling of the
diastereotopic hydrogens to each other and to phos-
phorus [11]. The presence of the sulfur ligand pre-
vents coupling to phosphorus in cis,cis- and the cis half
of cis,trans-9 as observed for cis-Cp(CO)2(PPh3)-
WSCH2Ph [4c,d], and only two doublets (J=12 Hz) can
be assigned to each of these environments (the two halves
of both the D,L- and meso-cis,cis isomers are equivalent).
Trans,trans-9 is highly symmetric and therefore exhibits
only one doublet (JP–H=1.7 Hz). Finally, the trans half
of cis,trans-9 is diastereotopic due to its chiral cis half
and apparently is the only species in this system which
exhibits a full ABX resonance pattern. The fulvalene
region of the spectrum displays the expected 18 multiplets
[8g] relatively well resolved.
The IR spectra of complexes 8–10 exhibited two
absorbances in the 1927–1944 (s) and 1846–1862 (vs)
cm−1 regions. The band positions indicated a decrease
in the ligand basicity in the order of SiPr\SCH2Ph\
SPh, while the relative intensities of the bands pointed
to an increasing trans/cis isomeric ratio in the same
1
order. H- and 31P{1H}-NMR investigations provided
evidence for the presence of all four isomers in equili-
brated solutions (Scheme 3), their relative ratio being
considerably effected by the solvent used. For example,
the ratio of the isomers of complex 9 in CD2Cl2 was 16%
cis,cis (1:1 mixture of D,L and meso), 47% cis,trans and
37% trans,trans (40:60 total cis:trans ratio), but in
DMSO-d6 it was 39% cis,cis (1:1 mixture of D,L and
meso), 40% cis,trans and 21% trans,trans (60:40 total
cis:trans ratio). Thus, the cis,trans form remains domi-
nant (40–50%) for complex 9. Similar results were
obtained in acetone-d6 solution for complex 10 (33:67
total cis:trans ratio).
2.3. Synthesis and characterization of bishydrosulfido
complexes F6W2(CO)4L2(SH)2 (L=CO, PPh2Me)
FvW2(CO)6(SH)2 (11) was generated in solution by
treating 2 with a stoichiometric amount of S8 [3b]. Unlike
its cyclopentadienyl analogue, however, 11 proved to be
unstable and decomposed to give FvW2(CO)6(W–W).
Complex 11 was characterized in solution by IR (Table
1), 1H- and 13C{1H}-NMR spectroscopy and the data are
fully consistent with the proposed structure. The SH
proton resonance was detected at l −2.28 (JW–H=4.6
Hz) in C6D6, slightly downfield from that observed for
CpW(CO)3SH (l −2.51 [3b]).
1
While a single one-dimensional H-NMR spectrum is
usually not enough to characterize isomeric mixtures of
fulvalene complexes, that of complex 9 recorded at
high-field (500 MHz) in CD2Cl2 solution was extraordi-
narily informative due to the coexistence of several
conditions: (1) significant amounts of all four isomers at
equilibrium that do not undergo fast exchange on the
NMR time scale; (2) relatively well resolved resonances;
and (3) the methylene region exhibited an interesting
resonance pattern due to the diastereotopic methylene
While the reactions proceeded instantly in polar sol-
vents such as THF or acetone-d6, those carried out in

36
I. Ko6a´cs, A. Sha6er / Journal of Organometallic Chemistry 586 (1999) 31–40
resonances different from those of 2 and 11, respec-
tively, as well as four fulvalene pseudotriplets at l 4.24,
4.50, 4.66, and 4.80 with appropriate integral ratios.
These results suggest that the insertion of sulfur into
C6D6 resulted in a mixture of 2, 11 and the mixed
hydrido–hydrosulfido intermediate FvW2(CO)6(SH)H.
1
Its H-NMR spectrum exhibited both hydridic (l −
6.89, JW–H=37 Hz) and SH (l −2.31, JW–H=4.6 Hz)
Fig. 1. 1H-NMR (500 MHz) spectrum of FvW2(CO)4(PPh2Me)2(SCH2Ph)2 in CD2Cl2. (a) PMe resonances; (b) SCH2– resonances; (c) fulvalene
resonances: cis,cis isomers, 2H each ( ), cis,trans isomer, 1H each (ꢀ), trans,trans isomer, 4H each (ꢁ).

I. Ko6a´cs, A. Sha6er / Journal of Organometallic Chemistry 586 (1999) 31–40
37
the two W–H bonds of 2 takes place in two distinc-
tive steps. Note that FvW2(CO)6(SH)H is formally the
product of the oxidative cleavage of the metal–metal
bond in FvW2(CO)6(W–W) by H2S. Treatment of 11
with CS2 gave only the dimer FvW2(CO)6(W–W) as
extreme care must be exercised when working with
H2S, which is very toxic and has a bad odor. The
reactions must be conducted in a well-ventilated fume
hood and every effort must be made to ensure con-
tainment of the gas. The recommended procedure for
drying and handling H2S is described in the literature
[14]). IR spectra were recorded on a Bruker IFS 48
spectrometer in solutions using a 0.1 mm NaCl cell.
1H-, 13C{1H}-, and 31P{1H}-NMR measurements were
performed on a Jeol CPF 270 spectrometer. FAB(+)
mass spectra were obtained on a Kratos MF25RFA
instrument using 2-nitrobenzyl alcohol as the matrix.
Elemental analyses were carried out by the ‘Labora-
toire d’Analyse Elementaire’ at the University of Mon-
treal.
1
detected by H-NMR spectroscopy. On the basis of IR
band positions (Table 1), the basicity of SH is com-
parable to that of SPh, while the reactive SiPr and
SCH2Ph groups are consistently stronger bases.
Similar treatment of 3 with S8 in THF gave only
slow degradation, but the reaction of 10 with H2S
gave FvW2(CO)4(PPh2Me)2(SH)2 (12). This is
analogous to the treatment of CpW(CO)2(PPh3)SR
with H2S to generate CpW(CO)2(PPh3)SH [4c]. Com-
plex 12 crystallized with THF in the lattice (NMR)
from a H2S saturated solution of 10 at r.t. Unlike
8–10, these orange crystals were quite soluble in chlo-
3.1. (Et4N)2[F6W2(CO)6] (1)
1
rinated hydrocarbons. A H-NMR spectrum of freshly
dissolved 12 in CDCl3 exhibited eight multiplets in the
fulvalene region, which is typical for a 1:1 mixture of
D,L- and meso-cis,cis isomers, as well as two doublets
in both the PMe and SH region. A 31P{1H}-NMR
spectrum of this sample exhibited two closely spaced
singlet resonances in the upfield region at l 4.97 and
5.07, consistent with the 1H-NMR observation. In
time new resonances appeared in the spectra indicating
a relatively fast isomerization process, which was com-
plete in about 3 h at r.t. The equilibrium mixture
consisted of 22% D,L-cis,cis, 22% meso-cis,cis, 45%
cis,trans and 11% trans,trans isomer (total cis:trans
ratio 66:34). In addition to those of the cis,cis isomer,
three new phosphorus signals were present at l 5.20
and 14.8 (cis,trans), and 15.0 (trans,trans) in the
31P{1H}-NMR, as well as three new SH and PMe
A freshly prepared solution of Li2[C10H8] (30 mmol)
in 264 ml of THF/hexane (9:1) [8g] was transferred by
cannula into a three-neck round-bottom flask contain-
ing a mixture of W(CO)3(EtCN)3 (26 g, 60 mmol) and
Et4NBr (12.6 g, 60 mmol). The resulting slurry in-
stantly turned brown in color. It was refluxed with
stirring for 1 h to complete the reaction. The solvent
was evaporated under reduced pressure, leaving a
sticky brown residue which was washed with hexane
and dried in vacuum. The crude product was washed
with several 50 ml portions of ether until the washings
were colorless, leaving a yellow–brown solid. After
drying under reduced pressure for several hours, 45 g
of an extremely fine, tan powder was collected (65%
pure). 1H-NMR (acetone-d6): l 1.35 (tt, J=7.2, 1.7
Hz, 24H, CH3), 3.43 (q, J=7.2 Hz, 16H, CH2N),
4.78, 5.24 (both ‘t’, J=2.3 Hz, 4H, Fv). 13C{1H}-
NMR (acetone-d6): l 82.4, 84.45 (both Fv), 103.2 (Fv
C-1), 227.4 (CO).
1
doublets in the H-NMR spectra, the former exhibit-
ing characteristic couplings to cis and trans phospho-
rus atoms while the latter being in positions quite
typical for cis and trans phosphines (the cis is upfield
from trans).
Complexes 11 and 12 were surprisingly unreactive
toward SO2. THF and CH2Cl2 solutions of these com-
plexes were treated with a large excess of SO2 gas at
r.t. and the reactions were monitored by IR spec-
troscopy. Complex 12 remained unchanged for at least
3 days at r.t. Complex 11 slowly decomposed to an
insoluble precipitate (ca. 50% conversion in 1 day).
3.2. F6W2(CO)6H2 (2)
A vigorously stirred slurry of 1 (10 g) containing
NaI and LiBr impurities in 50 ml of toluene was
treated with 4 ml of glacial acetic acid at r.t. The
solids were allowed to settle and the clear, yellow–
brown solution was transferred into another flask by
cannula. The residues were suspended in 10 ml of
toluene for 5 min, allowed to settle and the superna-
tant transferred. This process was repeated until nearly
colorless supernatant solutions formed to give 150 ml
3. Experimental
All manipulations were carried out under an inert
atmosphere (N2 or Ar), using standard Schlenk tech-
niques and a drybox. Solvents were dried and freshly
distilled under nitrogen prior to use. W(CO)3(EtCN)3
[12], N-phenyl-, benzyl- and (2-propyl)phthalimide [13]
were prepared according to literature procedures. H2S
and SO2 were purchased from Matheson (Caution:
1
combined toluene solution of 2. H-NMR (toluene-d8):
l −6.96 (JW–H=37 Hz, 2H, WH), 4.48, 4.80 (both
1
‘t’, J=2.3 Hz, 4H, Fv). H-NMR (acetone-d6): l −
6.99 (JW–H=38 Hz, 2H, WH), 5.69, 6.23 (both ‘t’,
J=2.3 Hz, 4H, Fv). 13C{1H}-NMR (acetone-d6) l
86.8, 87.7 (Fv), 102.8 (Fv C-1), 216.1 (CO).

38
I. Ko6a´cs, A. Sha6er / Journal of Organometallic Chemistry 586 (1999) 31–40
3.5. Li2[F6W2(CO)4(PPh2Me)2] (4)
3.3. F6W2(CO)4(PPh2Me)2H2 (3)
A solution of 3 (1.0 g, 0.99 mmol) in 20 ml of THF
was stirred and cooled to −10°C. Then 1.5 ml of a 1.4
M solution of methyllithium in ether (Aldrich) was
added dropwise by means of a syringe. The yellow
starting solution instantly became red upon addition of
the first drops of methyllithium. After completing the
addition, the mixture was allowed to warm to r.t. and
stirred for 1 h while a yellow precipitate formed. It was
filtered, washed with hexane and dried under reduced
pressure. Yield: 1.0 g (0.98 mmol, 98%). 1H-NMR
(CD3CN): l 2.05 (d, J=8 Hz, 6H, PMe), 4.50, 4.96
(both m, 4H, Fv), 7.20 (m, 12H, m,p-Ph), 7.49 (m, 8H,
o-Ph). 13C{1H}-NMR (CD3CN): l 23.7 (PMe), 81.2,
83.7 (both Fv), 101.9 (Fv C-1), 127.05 (d, JP–C=7.3
Hz, m-Ph), 129.1 (p-Ph), 131.8 (d, JP–C=11 Hz, o-
Ph). 31P{1H}-NMR (CD3CN): l 28.8.
To a solution of 2 in 150 ml of toluene (prepared in
situ from 10 g of crude 1), 2.7 ml methyldiphenylphos-
phine was injected and the mixture was heated at
105–110°C overnight by means of an oil bath. At this
point, an IR spectroscopic analysis of the reaction
mixture showed complete consumption of 2 and for-
mation of 3 as the sole product. The yellow solution
was filtered through Celite and evaporated to dryness.
The resulting solid was washed with hexane and recrys-
tallized from toluene at −30°C to yield 5.0 g (4.95
mmol, 70% based on W(CO)3(EtCN)3) of yellow 3.
Anal Calc. for C40H36O4P2W2: C, 47.55; H, 3.59.
1
Found: 47.65; H, 3.64%. H-NMR (acetone-d6): l −
7.08 (d, JP–H=55, JW–H=48 Hz, 2H, WH), 2.22 (d,
JP–H=8.6 Hz, 6H, PCH3), 4.94–5.43 (br m, 8H, Fv),
7.40 (br m, 12H, m,p-Ph), 7.51 (m, 8H, o-Ph).
13C{1H}-NMR (acetone-d6): l 86.3, 87.6 (br, Fv), 128.2
(d, JP–C=9.4 Hz, m-Ph), 129.7 (p-Ph), 131.8 (d, JP–
C=10 Hz, o-Ph). 31P{1H}-NMR (acetone-d6): l 17.5
(br).
Yellow–brown solutions of 4 quickly changed color
to dark red when briefly exposed to air. The resulting
organometallic
product
was
identified
as
FvW2(CO)4(PPh2Me)2(W–W) on the basis of spectro-
1
scopic data. H-NMR (CD3CN): l 4.32 (m, 4H, Fv),
4.62 (‘t’, 4H, Fv). 31P{1H}-NMR (CD3CN) l 20.5.
3.4. F6W2(CO)4(PPh2Me)2I2
The dihydride 3 (1.5 g, 1.48 mmol) was dissolved in
50 ml of toluene and solid iodoform (1.2 g, 3.05 mmol)
was added to the stirred solution at r.t. The original
yellow color quickly changed to orange and a red
microcrystalline solid formed overnight. The mixture
was concentrated to about 10 ml under reduced pres-
sure and hexane was added to complete the precipita-
tion. The solid product was filtered, washed with
hexane and dried under vacuum. Yield: 1.8 g (1.41
mmol, 95%). For an alternative preparation see Ref.
3.6. General synthesis of F6W2(CO)6(SR)2 (R=i-Pr
(5), CH2Ph (6), Ph (7))
To a slurry of 1 (6.0 g, 4.3 mmol) in 100 ml of THF,
8.6 mmol RSphth was added at once at r.t. The reac-
tion mixtures instantly became yellow–orange and
were stirred overnight. The resulting mixtures were
filtered through Celite and the filtrates were evaporated
to dryness. The orange–brown solids were washed
with hexane and dried under reduced pressure. Re-
peated recrystallization from CH2Cl2 did not provide
analytically pure samples due to contamination by
Et4Nphthalimide. All compounds were identified by
spectroscopic techniques.
1
[7a]. The H-NMR data and assignments reported be-
low revise those reported in [7a].
Cis,cis isomers (D,L-/meso-=1:1, 24%); 1H-NMR
(CDCl3): l 2.46 (d, JP–H=8.2 Hz, 6H, PMe), 2.48 (d,
J
P–H=8.7 Hz, 6H, PMe), 4.81 (m, 2H, Fv), 4.90 (m,
Data for 5: FAB(+)-MS: m/z (%) [M]+ =814(0.9).
1H-NMR (acetone-d6): l 1.17 (d, J=6.7 Hz, 12H,
CH3), 2.63 (sept, J=6.7 Hz, 2H, CHS), 5.85, 6.25
(both ‘t’, J=2.3 Hz, 4H, Fv). 13C{1H}-NMR (acetone-
d6): l 27.0 (CH3), 36.3 (CHS), 91.3, 93.2 (both Fv),
108.1 (Fv C-1), 214.1 (CO cis to S), 226.5 (CO trans to
S).
2H, Fv), 5.10 (m, 2H, Fv), 5.19 (m, 4H, Fv), 5.26 (m,
2H, Fv), 5.67 (m, 2H, Fv), 5.73 (m, 2H, Fv), 7.40–7.67
(m, Ph). 31P{1H}-NMR (CDCl3): l −4.44, −4.31.
1
Cis,trans isomer (59%); H-NMR (CDCl3): l 2.36 (d,
JP–H=9.0 Hz, PMe, trans), 2.43 (d, JP–H=8.4 Hz,
PMe, cis), 4.66 (m, 1H, Fv, trans), 4.75 (m, 1H, Fv,
trans), 4.90 (m, 1H, Fv, cis), 4.95 (m, 1H, Fv, trans),
5.00 (m, 1H, Fv, trans), 5.14 (m, 1H, Fv, cis), 5.19 (m,
1H, Fv, cis), 5.79 (m, 1H, Fv, cis), 7.40–7.67 (m, Ph).
31P{1H}-NMR (CDCl3): l −4.26 (cis), 10.26 (trans).
Data for 6: FAB(+)-MS: m/z (%) [M]+ =910(0.5).
1H-NMR (acetone-d6): l 3.46 (s, 4H, CH2), 5.71, 6.18
(both ‘t’, J=2.3 Hz, 4H, Fv), 7.17–7.42 (m, 10H, Ph).
13C{1H}-NMR (CD2Cl2): l 36.8 (CH2S), 90.6, 91.9
(both Fv), 106.5 (Fv C-1), 123.4, 128.4, 129.0, 134.3
(all Ph).
1
Trans,trans isomer (17%); H-NMR (CDCl3): l 2.34
(d, JP–H=9.1 Hz, 6H, PMe), 4.81, 5.00 (both m, 4H,
Fv), 7.40–7.67 (m, Ph). 31P{1H}-NMR (CDCl3): l
10.53.
1
Data for 7: H-NMR (acetone-d6): l 5.87, 6.41 (both
‘t’, J=2.3 Hz, 4H, Fv), 7.16 (m, 10H, Ph).

I. Ko6a´cs, A. Sha6er / Journal of Organometallic Chemistry 586 (1999) 31–40
39
3.7. Reactions of complexes 5–7 with CS2
methods.
Data for 8: FAB(+)-MS: m/z (%) [M]+ =1159(0.5).
Data for 9: FAB(+)-MS: m/z (%) [M]+ =1254(0.3).
Cis,cis isomer (D,L-/meso-=1:1, 16%); 1H-NMR
(CD2Cl2): l 2.00 (d, JP–H=8.7 Hz, 6H, PCH3), 2.04 (d,
NMR scale experiments were carried out with sam-
ples containing 0.05 mmol of complexes 5–7 dissolved
in 0.7 ml of acetone-d6 and 60 ml of CS2. Reactions
proceeded slowly at r.t. with 5 and 6 as indicated by a
gradual color change from brown to cherry red. No
change in color was observed for 7 in 2 weeks. The
transformations were monitored by 1H-NMR spec-
troscopy. In a quantitative reaction, first the monoin-
sertion product RS(CO)3W(m-Fv)W(CO)2S2CSR (A)
was formed, followed several hours later by
FvW2(CO)4(S2CSR)2 (B). Formation of the latter was
complete in 3 days for 5 and 2 weeks for 6. No reaction
took place with 7.
JP–H=8.6 Hz, 6H, PCH3), 3.176 (d, J=12 Hz, 2H,
CH2), 3.182 (d, J=12 Hz, 2H, CH2), 3.58 (d, J=12
Hz, 2H, CH2), 3.61 (d, J=12 Hz, 2H, CH2), 5.06 (m,
2H, Fv), 5.12 (m, 4H, Fv), 5.19 (m, 2H, Fv), 5.24 (m,
4H, Fv), 5.33 (m, 2H, Fv), 5.36 (m, 2H, Fv), 6.96–7.51
(m, Ph). 31P{1H}-NMR (CD2Cl2): l 5.27, 5.34.
1
Cis,trans isomer (47%); H-NMR (CD2Cl2): l 1.92
(d, JP–H=8.5 Hz, 3H, PCH3, cis), 2.40 (d, JP–H=8.9
Hz, 3H, PCH3, trans), 2.97 (d, J=12 Hz, 1H, CH2,
cis), 3.48 (dd, JP–H=1.7 Hz, J=12 Hz, 1H, CH2,
trans), 3.52 (d, J=12 Hz, 1H, CH2, cis), 3.59 (dd,
Data for 5A: 1H-NMR (acetone-d6): l 1.18, 1.42
(both d, J=6.7 Hz, 6H, CH3), 2.633, 3.99 (both sept,
J=6.7 Hz, 1H, CHS), 5.74, 5.79, 6.08, 6.28 (all ‘t’,
J=2.3 Hz, 2H, Fv).
J
P–H=1.7 Hz, J=12 Hz, 1H, CH2, trans), 4.45, 4.60,
4.71 (all m, 1H, Fv), 4.92 (m, 2H, Fv), 5.10, 5.39, 5.51
(all m, 1H, Fv), 6.96–7.51 (m, Ph). 31P{1H}-NMR
(CD2Cl2): l 6.2 (cis), 13.2 (trans).
Data for 5B: FAB(+)-MS: m/z (%) [M]+
=
1
1
910(1.2). H-NMR (acetone-d6): l 1.43 (d, J=6.7 Hz,
12H, CH3), 3.99 (sept, J=6.7 Hz, 2H, CHS), 5.70, 6.13
(both ‘t’, J=2.3 Hz, 4H, Fv). 13C{1H}-NMR (acetone-
d6): l 22.0 (CH3), 38.0 (CH), 88.7, 90.8 (both Fv), 108.2
(Fv C-1), 243.2 (CO).
Trans,trans isomer (37%); H-NMR (CD2Cl2): l 2.36
(d, JP–H=8.9 Hz, 6H, PCH3), 3.39 (d, JP–H=1.7 Hz,
4H, CH2), 4.71, 4.75 (both m, 4H, Fv), 6.96–7.51 (m,
Ph). 31P{1H}-NMR (CD2Cl2): l 13.4.
Data for 10: cis,cis isomers (D,L-/meso- 1:1, 9%);
1H-NMR (acetone-d6): l 2.23 (d, JP–H=8.6 Hz, 6H,
PCH3), 2.27 (d, JP–H=8.4 Hz, 6H, PCH3). The other
proton resonances of this minor component extensively
overlapped with those of the major cis,trans and
trans,trans isomers. 31P{1H}-NMR (acetone-d6): l 5.9.
Data for 6A: 1H-NMR (acetone-d6): l 3.48, 4.46
(both s, 2H, CH2), 5.62, 5.72, 5.92, 6.25 (all ‘t’, J=2.3
Hz, 2H, Fv), 7.17–7.52 (m, 10H, Ph).
1
Data for 6B: H-NMR (acetone-d6): l 4.50 (s, 4H,
CH), 5.64, 5.96 (both ‘t’, J=2.3 Hz, 4H, Fv), 7.17–
7.52 (m, 10H, Ph).
1
Cis,trans isomer (48%); H-NMR (acetone-d6): l 2.17
(d, JP–H=8.6 Hz, 3H, PCH3, cis), 2.42 (d, JP–H=8.9
Hz, 3H, PCH3, trans), 4.65 (m, 2H, Fv), 4.96, 5.22,
5.32, 5.41, 5.75, 5.90 (all m, 1H, Fv), 6.8–7.5 (m, Ph).
31P{1H}-NMR (acetone-d6): l 5.9 (cis), 12.4 (trans).
3.8. General synthesis of F6W2(CO)4(PPh2Me)2(SR)2
(R=i-Pr (8), CH2Ph (9), Ph (10))
1
Dihydride 3 (2.0 g, 2.0 mmol) was dissolved in 100
ml of THF and treated with 3 ml of a 1.4 M solution of
methyllithium in ether (Aldrich) at −10°C, resulting in
a color change from yellow to red. The solution was
allowed to warm to r.t. and stirred for 2 h to complete
the reduction process, which was indicated by the for-
mation of 4 as a yellow precipitate. The mixture was
cooled below 0°C and treated with 4.0 mmol of crys-
talline RSphth. Stirring overnight under ambient condi-
tions led to an orange slurry, which was filtered
through Celite and the filtrate was concentrated under
reduced pressure. Adding hexane gave a precipitate
which was collected and dried under reduced pressure
to give orange microcrystalline products. These were
poorly soluble in a variety of solvents, including hot
THF, toluene, DMSO and CH2Cl2 and could not be
purified. Satisfactory elemental analysis data were ob-
tained only for 9 which was recrystallized from CH2Cl2
with significant loss. Anal Calc. for C54H48O4P2S2W2:
C, 51.69; H, 3.86; S, 5.11. Found: 48.59; H, 3.82; S,
4.94%. All complexes were identified by spectroscopic
Trans,trans isomer (43%); H-NMR (acetone-d6): l
2.38 (d, JP–H=8.9 Hz, 6H, PCH3), 4.85, 5.22 (both m,
4H, Fv), 6.8–7.5 (m, Ph). 31P{1H}-NMR (acetone-d6):
l 12.7.
3.9. F6W2(CO)6(SH)2 (11)
To a solution of 2 (40 mg, 0.06 mmol) in 0.7 ml
acetone-d6 4 mg (0.12 mmol) of S8 was added at once at
r.t. The reaction mixture instantly changed color from
yellow to orange and complete transformation of 2 into
11 was confirmed by NMR spectroscopy. Similar reac-
tions were carried out in THF and C6D6 solutions.
Complex 11 readily converts to FvW2(CO)6(W–W) in
these media and could not be purified. 1H-NMR
(C6D6): l −2.28 (JW–H=4.6 Hz, 2H, WSH), 4.34 (‘t’,
J=2.3 Hz, 4H, Fv), 4.76 (‘t’, J=2.3 Hz, 4H, Fv).
1H-NMR (acetone-d6): l −2.34 (s, 2H, SH), 5.81 (‘t’,
J=2.3 Hz, 4H, Fv), 6.27 (‘t’, J=2.3 Hz, 4H, Fv).
13C{1H}-NMR (acetone-d6): l 90.0, 92.9 (Fv), 110.2
(Fv C-1), 214.4 (CO cis to S), 226.8 (CO trans to S).

40
I. Ko6a´cs, A. Sha6er / Journal of Organometallic Chemistry 586 (1999) 31–40
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3.10. F6W2(CO)4(PPh2Me)2(SH)2 (12)
A THF solution of 9 was prepared as described
above and saturated with H2S at r.t. An IR analysis of
the reaction mixture indicated no reaction at first so it
was allowed to stand for 1 week. During this period
orange–yellow crystals separated, which were filtered
and dried under reduced pressure. They were soluble in
1
chlorinated hydrocarbons. A H-NMR analysis of the
crystalline material suggested that they contained THF
of crystallization.
Cis,cis isomers (D,L-/meso-=1:1, 44%); 1H-NMR
(CDCl3): l −2.35 (d, JP–H=17 Hz, 2H, SH), −2.32
(d, JP–H=17 Hz, 2H, SH), 2.14 (d, JP–H=8.2 Hz, 6H,
PCH3), 2.16 (d, JP–H=8.4 Hz, 6H, PCH3), 5.00 (m,
4H, Fv), 5.16 (m, 2H, Fv), 5.21 (m, 2H, Fv), 5.24 (m,
2H, Fv), 5.27 (m, 2H, Fv), 5.40 (m, 2H, Fv), 5.54 (m,
2H, Fv), 7.38 (m, 40H, Ph). 31P{1H}-NMR (CDCl3): l
4.97, 5.07.
1
Cis,trans isomer (45%); H-NMR (CDCl3): l −2.41
(d, JP–H=17 Hz, 1H, SH, cis), −2.29 (d, JP–H=1.7
Hz, 1H, SH, trans), 2.13 (d, JP–H=8.4 Hz, 3H, PCH3,
cis), 2.35 (d, JP–H=8.9 Hz, 3H, PCH3, trans), 4.60 (m,
1H, Fv), 4.74 (m, 2H, Fv), 4.85 (m, 1H, Fv), 5.04, 5.20,
5.33, 5.66 (all m, 1H, Fv), 7.37 (m, 10H, Ph, cis), 7.45
(m, 10H, Ph, trans). 31P{1H}-NMR (CDCl3): l 5.20
(cis), 14.79 (trans).
1
Trans,trans isomer (11%); H-NMR (CDCl3): l −
2.36 (d, JP–H=1.7 Hz, 2H, SH), 2.33 (d, JP–H=8.9 Hz,
6H, PCH3), 4.72, 4.98 (both m, 4H, Fv), 7.45 (m, 20H,
Ph). 31P{1H}-NMR (CDCl3): l 15.03.
Acknowledgements
We thank the Natural Sciences and Engineering Re-
search Council of Canada (NSERC) and the Quebec
Department of Education for financial support.
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