Synthesis, structure, and reactivity of group 14 bid (thiophosphinoyl) metal complexes

Article abstract of DOI:10.1021/om9008923

Bis(thiophosphinoyl)methane, CH₂(PPh₂=S)₂, and its monolithium salt [Li{(S=PPh₂)₂CH}-(THF)(Et ₂O)] (1) have been used to prepare a series of low-valent group 14 metal complexes. The reaction of lithium salt [Li{(S=PPh₂) ₂CH}(THF)(Et₂O)] (1) with 1 equiv of MCl₂ (M = Ge, Sn) in diethyl ether afforded monomeric organometal(II) chlorides [MCl{CH(PPh₂=S)₂}] (M = Ge (2), Sn (3)). Treatment of CH₂(PPh₂=S)₂ with equimolar M(N(SiMe ₃)₂}₂ (M = Sn, Pb) afforded 1,3-dimetallacyclobutanes [M(μ²-C(Ph₂P=S) ₂}]₂ (M = Sn (4), Pb (5)), which are believed to be formed by the dimerization of the metallavinylidene intermediate. Compounds 2 and 5 further reacted with elemental chalcogens (S and Se) to give trans-dithiadigermetane [GeCl(CH(PPh₂=S)₂}(μ-S)] ₂ (6) and lead(II) chalcogenates [PbE{C(PPh₂=S) ₂}] (E = S (7), Se (8)), respectively. Compounds 2-8 have been determined by X-ray crystallography.

Full text of DOI:10.1021/om9008923

814 Organometallics 2010, 29, 814–820
DOI: 10.1021/om9008923
Synthesis, Structure, and Reactivity of Group 14 Bis(thiophosphinoyl)
Metal Complexes
Wing-Por Leung,* Chi-Ling Wan, Kwok-Wai Kan, and Thomas C. W. Mak
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong,
China
Received October 13, 2009
Bis(thiophosphinoyl)methane, CH2(PPh2dS)2, and its monolithium salt [Li{(SdPPh2)2CH}-
(THF)(Et2O)] (1) have been used to prepare a series of low-valent group 14 metal complexes. The
reaction of lithium salt [Li{(SdPPh2)2CH}(THF)(Et2O)] (1) with 1 equiv of MCl2 (M=Ge, Sn) in
diethyl ether afforded monomeric organometal(II) chlorides [MCl{CH(PPh2dS)2}] (M=Ge (2), Sn
(3)). Treatment of CH2(PPh2dS)2 with equimolar M{N(SiMe3)2}2 (M = Sn, Pb) afforded 1,3-
dimetallacyclobutanes [M{μ2-C(Ph2PdS)2}]2 (M = Sn (4), Pb (5)), which are believed to be formed
by the dimerization of the metallavinylidene intermediate. Compounds 2 and 5 further reacted with
elemental chalcogens (S and Se) to give trans-dithiadigermetane [GeCl{CH(PPh2dS)2}(μ-S)]2 (6) and
lead(II) chalcogenates [PbE{C(PPh2dS)2}] (E=S (7), Se (8)), respectively. Compounds 2-8 have
been determined by X-ray crystallography.
Introduction
from the ligand to the metal center have been observed.2-8
Recently, Le Floch’s group reported the synthesis of a dianionic
complex from bis(diphenylthiophosphinoyl)methane.9 This
dianionic complex has been used as a precursor to synthe-
size various transition metal and rare earth metal carbene
complexes.10-15
Despite numerous thiophosphinoyl transition metal, lantha-
nide, and actinide complexes, group 14 compounds bearing a
thiophosphinoyl ligand are scarce.16,17 We have reported the
synthesis of some group 14 metal complexes derived from the
isoelectronic phosphoranoimino ligands, including the novel
bisgermavinylidene and dimetallacyclobutanes, recently.18 In
Compounds derived from thiophosphinoyl ligands have been
studied since the 1970s.1 Phosphoranosulfides, R3PdS, can be
depronated to form anionic ligands, which can serve as versatile
ligands for transition metals, lanthanides, and actinides. A series
of metal complexes have been prepared from the deprotonated
iminobis(phosphoranosulfide). Both η2- and η3-coordinations
*Corresponding author. E-mail: kevinleung@cuhk.edu.hk.
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pubs.acs.org/Organometallics
Published on Web 01/15/2010
2010 American Chemical Society

Article
Organometallics, Vol. 29, No. 4, 2010 815
Scheme 1
This may be because the extremely bulky ligand makes the
formation of the trans-isomer more favorable.
Similar structures of dithiadigermetanes [(Tbt)(Mes)Ge(μ-
S)]2 (Tbt = 2,4,6-tris(bis(trimethylsilyl)methyl)phenyl, Mes =
2,4,6-trimethylphenyl) and [(Bbt)(Br)Ge(μ-S)]2 (Bbt=2,6-bis-
(bis(trimethylsilylmethyl)-4-(tris(trimethylsilyl)methyl)phenyl)
have been reported from the desulfurization of tetrathiagermo-
lane and sulfurization of digermene, respectively.19-24 It was
suggested that they were also formed by the rapid dimerization
of the intermediary germanethione or germathiocarbonyl bro-
mide. X-ray structure analysis indicated that the cis-configura-
tion with a folded rhombic Ge2S2 ring is found in these two
compounds.
Treatment of 5 with stoichiometric amounts of elemental
chalcogens in toluene did not give group 14 ketone or ketene
analogues (R2PbdE or >CdPbdE). Instead, two novel
lead(II) chalcogenate complexes [PbE{C(Ph2PdS)2}] (E =
S (7) and Se (8)) were obtained (Scheme 4). It is believed that
the chalcogen atom inserted in the CdPb: bond to form a
>C-E-Pb: moiety. This result differs markedly from the
synthesis of group 14 dialkylmetal chalcogenones R2MdE
(R = CH(SiMe3)C9H6N-8 or CPh(SiMe3)C5H4N-2; M =
Ge or Sn)25 and chalcogen-bridged dimers of germaketene
analogues [(Me3SiNdPPh2)2CdGe(μ-E)]2 (E = S, Se, and
Te).18c This may be explained by the “inert pair effect”,
which makes the electron pair on the lead(II) center less
favorable for bond formations. Compound 8 is light sensitive
and turns black on exposure to light; therefore it was
prepared in the absence of light. Compounds 7 and 8 are
believed to exist as zwitterions, as supported by the spectro-
scopic data in the next section.
Spectroscopic Properties. Compounds 2-8 were isolated
as air- and moisture-sensitive colorless, yellow, and red crystal-
line solids. They have been characterized by NMR spectros-
copy and elemental analysis. The 1H NMR spectra of 2 and 3
both displayed one set of signals due to the ligand backbone. A
triplet [δ 3.83 (br) (2); δ 4.20 ppm (JP-H = 13.5 Hz) (3)] was
observed for the methanide proton on the P-C-P backbone.
The 13C NMR spectra of 2 and 3 are normal. The 31P NMR
spectra showed two singlets [δ 33.81, 39.95 (2); δ 33.82, 37.63
ppm (3)] due to two different phosphorus environments,
consistent with the solid-state structures. This indicates that
the coordination of the sulfur atoms of the phosphinothioyl
groups to the metal centers in 2 and 3 is nonfluxional in
solution. The 119Sn NMR spectrum of compound 2 displayed
a signal at δ -129.58 ppm (2JSn-P = 169 Hz), which is com-
parable to that of δ -224 ppm in [{HC(CMeNAr)2}SnCl]26
and δ -197.95 ppm in [Sn{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-
2)}Cl].27 This indicates that the tin metal center is probably
three-coordinate in solution.
this paper, we report some group 14 thiophosphinoyl
metal(II) chlorides and 1,3-dimetallacyclobutanes from bis-
(thiophosphinoyl)methane. Further reactions of these com-
pounds with elemental chalcogens will also be described.
Results and Discussion
Synthesis of Chlorogermylene and Chlorostannylene. The
monolithium salt [Li{(SdPPh2)2CH}(THF)(Et2O)] (1) was
used as the ligand transfer reagent. It was prepared by the
reaction of CH2(PPh2dS)2 with BunLi in THF. Compound 1
has been characterized by NMR spectroscopy, elemental
analysis, and X-ray crystallography. Metathesis reaction of 1
with 1 equiv of MCl2 (M = Ge, Sn) in Et2O afforded [MCl-
{CH(PPh2dS)2}] (M=Ge (2), Sn (3)) (Scheme 1). On the
basis of the X-ray structures obtained, it was found that the
bonding mode of the thiophosphinoyl ligand is different
from that of the phosphoranoimino ligand [GeCl{(PPh2d
NSiMe3)2CH}] reported by our group.18c For the group 14
complex derived from the phosporanimine, the metal is
bonded to the ligand in a N,N chelate fashion. There are
no interactions between the metal centers and the methanide
carbons. It is probably due to the less bulky sulfur atom from
the ligand, which provides easier access for the coordination
to the metal.
Syntehsis of 1,3-Dimetallacyclobutanes. The reaction of
CH2(PPh2dS)2 with 1 equiv of M{N(SiMe3)2}2 (M = Sn, Pb)
in toluene afforded 1,3-distannacyclobutane [Sn{μ2-C(Ph2Pd
S)2}]2 (4) and 1,3-diplumbacyclobutane [Pb{μ2-C(Ph2PdS)2}]2
(5), respectively (Scheme 1). From the X-ray structures of the
products, it is suggested that the reaction undergoes the eli-
mination of hexamethyldisilazane to form a metallavinyli-
dene intermediate [:MdC(Ph2PdS)2] (M = Sn, Pb). It is then
followed by a head-to-tail cyclodimerization of unstable me-
tallavinylidene intermediate to form the 1,3-dimetallacyclobu-
tanes. Similar 1,3-dimetallacyclobutanes from phosphoranoi-
mine ligands have been reported by our group.18a,b,d,e
(19) Matsumoto, T.; Tokitoh, N.; Okazaki, R. J. Am. Chem. Soc.
1999, 121, 8811.
(20) Sasamori, T.; Sugiyama, Y.; Takeda, N.; Tokitoh, N. Orgnao-
metallics 2005, 24, 3309.
(21) Tokitoh, N.; Matsumoto, T.; Okazaki, R. Bull. Chem. Soc. Jpn.
1999, 72, 1665.
(22) Okazaki, R.; Tokitoh, N. Acc. Chem. Res. 2000, 33, 625.
(23) Tokitoh, N.; Okazaki, R. Adv. Organomet. Chem. 2001, 47, 121.
(24) Tokitoh, N.; Matsumoto, T.; Ichida, H.; Okazaki, R. Tetrahe-
dron Lett. 1991, 32, 6877.
(25) Leung, W.-P.; Kwok, W.-H.; Zhou, Z.-Y.; Mak, T. C. W.
Organometallics 2000, 19, 296.
Reaction of 2 and 5 with Chalcogens. The reaction of
germylene chloride (2) with an equimolar amount of sulfur
in THF gave the trans-dithiadigermetane [GeCl{CH(PPh2d
S)2}(μ-S)]2 (6) (Scheme 2), as confirmed by X-ray structure
analysis. It is believed that the germathiocarbonyl chloride
(6a) was formed as an intermediate. This intermediate exists
as resonance forms A and B in the mixture (Scheme 3). The
>GedS is so polar that it cannot be stabilized kinetically by
the ligand; that is, resonance form B contributes more. The
intermediate 6a underwent a head-to-tail dimerization to
give the product. Only the trans-compound was isolated.
(26) Ding, Y.; Roesky, H. W.; Noltemeyer, M.; Schmidt, H.-G.;
Power, P. P. Organometallics 2001, 20, 1190.
(27) Leung, W.-P.; So, C.-W.; Wu, Y.-S.; Li, H.-W.; Mak, T. C. W.
Eur. J. Inorg. Chem. 2005, 513.

816 Organometallics, Vol. 29, No. 4, 2010
Leung et al.
Scheme 2
Scheme 3
Scheme 4
electron pair at the metal centers. The MCPS four-membered
rings are nearly planar, as indicated by the sum of bond angles
(360.0ꢀ (2); 359.3ꢀ (3)). The coordinated P-S bond distances
[2.007(3) (2); 2.017(1) A (3)] are slightly longer than the
noncoordinated ones [1.954(2) (2); 1.959(1) (3) A], as the
electron density of P-S bonding is reduced by the SfM bond.
The Ge-C bond distance of 2.153(6) A in 2 is
similar to the Ge-C single-bond distance of 2.127(4) A
in [Ge{C(SiMe3)2C5H4N-2}2]28 and 2.135(4)
A
in
[Ge{CPh(SiMe3)C5H4N-2}2}].29 The Ge-Cl bond distance
of 2.288(2) A is comparable to that of 2.334(2) A
in [GeCl{(PPh2dNSiMe3)2CH}]18c and 2.295(12) A in
[{HC(CMeNAr)2}GeCl].26
The Sn-C bond distance of 2.374(2) A in 3 is very
close to the Sn-C single-bond distance of 2.35(2) A
Both 1H NMR and 13C NMR sprectra of 4 displayed one
set of signals due to the bis(thiophosphinoyl)methanediide
ligand. The 31P NMR spectrum of 4 showed a singlet at δ
32.01 ppm, which may be the result of fluxional coordination
of the thio sulfur atoms at tin centers in the solution.
in [Sn{C(SiMe3)2C5H4N-2}2]30,31 and 2.329(4)
A in
However, the 1H NMR and 13C NMR spectra of 5 showed a
different pattern. There are two sets of signals assignable to the
ligand backbone. Also, the 31P NMR spectra of 5 displayed
two singlets (δ 33.83, 35.72 ppm) due to two slightly different
phosphorus environments. The variable-temperature 31P
NMR of 5 in d8-THF has been carried out in the range from
60 to -60 ꢀC; the two peaks remained unchanged. The two
peaks did not coalesce at temperatures up to 60 ꢀC. We have
also recorded the 31P-31P EXSY NMR spectrum of 5 in d8-
THF. We did not find any cross-peak in the spectrum; there-
fore no exchange between the two phosphorus atoms is present.
We propose that the phosphorus atoms from two sets of
ligands within the molecule might have two slightly different
environments in solution. The 119Sn and 207Pb NMR signals in
compounds 4 and 5 have not been located. Similar results have
been found in the isoelectronic 1,3-dimetallocyclobutane de-
rived from the bis-phosphosphoranoimino ligand.18a,b
[Sn{CPh(SiMe3)C5H4N-2}2}].29 The Sn-Cl bond distances
of 2.521(1) A agrees well with the corresponding distance of
2.473(9) A in [{HC(CMeNAr)2}SnCl].26 The Sn-S distance
of 2.636(1) A is shorter than the average Sn-S distance of
2.735 A in [Me2Sn{(SPPh2)2N}2].16
The molecular structures of the 1,3-dimetallacyclobu-
tanes 4 and 5 are illustrated in Figures 2 and 3, respec-
tively. Selected bond distances (A) and angles (deg) are
listed in Table 4. In compound 4, two tin metal centers are
bridged by two methanediide carbon atoms to from a
planar 1,3-Sn2C2 four-membered ring. Additional coordi-
nation to the trigonal-pyramidal tin center from the thio
sulfur atoms of the ligand form SnCPS four-membered
rings. These SnCPS rings together with the Sn2C2 ring, as
the base, form a “step-like” structure framework. The
average Sn-C bond distances of 2.421 A is comparable
to that of 2.376 A in [Sn{μ2-C(Ph2PdNSiMe3)2}]2.18a The
Sn-Sn distance is too long to consider the presence of
bonding interaction. The average P-S bond distance of
2.010 A is slightly longer than that in the neutral ligand
(1.944 A).32
The 1H and 13C NMR spectra of 6 displayed signals
assignable to the ligand. There is a sharp singlet at δ 36.78
ppm in the 31P NMR spectrum of 6, which indicates all
phosphorus atoms share the same chemical environment in
solution. This agrees with the X-ray structure determined.
The 1H NMR and 13C NMR spectra of 7 and 8 are normal.
Two singlets [δ 31.87, 57.73 (7); δ 31.86, 59.39 ppm (8)] were
observed in their 31P NMR spectra. This indicates two phos-
phorus are in different environments and is consistent with the
fact that the zwitterions exist in equilibrium in solution. The
77Se NMR spectrum of compound 8 displayed a singlet at δ
893.34 ppm. To our knowledge, this is the first report of a 77Se
NMR chemical shift for lead(II) selenate compounds.
Compound 5 consists of two lead atoms bridged by
two methanediide carbon atoms to form a 1,3-Pb2C2 four-
membered ring, which is similar to compound 4. Two thio
sulfur atoms of the ligand are bonded to each lead center,
forming PbCPS rings. These PbCPS rings with the Pb2C2
as the base result in a “step-like” structure framework. This is
€
€
€
(28) Ossig, G.; Meller, A.; Bronneke, C.; Muller, O.; Schafer, M.;
X-ray Structures. Compounds 2 and 3 are heteroleptic
germylene and stannylene with similar structures. The mole-
cular structure of 2is shown in Figure 1. Selected bond distances
(A) and angles (deg) of 2 and 3 are listed in Table 3. In both
compounds, the metal center is bonded to the ligand in a C,S
chelate fashion and displays a trigonal-pyramidal geometry.
The angle sum at the germanium and tin centers is 271.7ꢀ and
254.2ꢀ, respectively, consistent with a stereochemically active
Herbst-Irmer, R. Organometallics 1997, 16, 2116.
(29) Leung, W.-P.; Kwok, W.-H.; Weng, L.-H.; Law, L. T. C.; Zhou,
Z. Y.; Mak, T. C. W. J. Chem. Soc., Dalton Trans. 1997, 4301.
(30) Engelhardt, L. M.; Jolly, B. S.; Lappert, M. F.; Raston, C. L.;
White, A. H. J. Chem. Soc., Chem. Commun. 1988, 336.
(31) Jolly, B. S.; Lappert, M. F.; Engelhardt, L. M.; White, A. H.;
Raston, C. L. J. Chem. Soc., Dalton Trans. 1993, 2653.
(32) Carmalt, C. J.; Cowley, A. H.; Decken, A.; Lawson, Y. G.;
Norman, N. C. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1996,
52, 931.

Article
Organometallics, Vol. 29, No. 4, 2010 817
ment with those in [(MesGe)2S2Cl2] (2.183(2) A),35 [{HC(CMe-
NAr)2}Ge(S)Cl] (2.195(7) A),38 and [Ge(S){N(SiMe3)C(Ph)-
C(SiMe3)(C5H4N-2)}Cl] (2.180(2) A).31
Compounds 7 and 8 are isostructural monomeric com-
plexes. The molecular structure of 7 is shown in Figure 5.
Selected bond distances (A) and angles (deg) of 7 and 8 are
listed in Table 6. Both compounds comprise a three-coordi-
nated lead center, with a chalcogen atom and two thio sulfur
atoms from the ligand. The bond angles around the Pb(II) cen-
ter [83.7(1)ꢀ, 82.6(1)ꢀ, 91.4 (1)ꢀ, — =257.7ꢀ (7); 83.0(1)ꢀ,
P
P
84.6(1)ꢀ, 93.1(1)ꢀ,
— = 260.7ꢀ (8)] suggest a trigonal-
pyramidal geometry and support the presence of a stereo-
chemically active lone pair. A six-membered PbS2P2C me-
tallacyle with a boat conformation, as shown in Figure 6, is
found. P(1), S(1), P(2), and S(2) lie in the best plane, with
C(1) and Pb(1) at the stern and bow position. The chalcogen
locked the boat conformation by bridging C(1) and Pb(1).
The CEPb plane is almost perpendicular to the P2S2 plane. It
is noteworthy that the C(1) atom in compounds 7 and 8 is
distorted from the expected trigonal-planar structure. This
can be indicated by the sum of angles around the carbon cen-
Figure 1. Molecular structure of 2; 30% thermal ellipsoids are
shown.
P
P
different from the “open-box”-like structure of [Pb{μ2-C-
(Ph2PdNSiMe3)2}]2.18a The lead center adopts four-coordi-
nated geometry with a distorted square-pyramidal environ-
ment. This is slightly different from the coordination of the tin
center in 4. The average Pb-C bond distance of 2.506 A is
comparable to that of 2.473 A in [Pb{μ2-C(Ph2PdNSi-
ter [ —=339.5ꢀ (7), —=339.1ꢀ (8)]. This may result from
the unusual cage formed. The average Pb-S bond distances
of 2.783 A in 7 and 2.782 A in 8 are comparable to that of
2.819 A in [Pb{(SPPh2)N}2].17 The P-C bond distances
[1.748(8), 1.725(8) (7); 1.749(1), 1.741(1) A (8)] and P-S
bond distances [2.031(3), 2.045(3) (7); 2.019(6), 2.060(6) A
(8)] in the two compounds are very similar, suggesting consi-
derable delocalization throughout the six-membered ring.
The lead-chalcogen bond [2.632(2) (7); 2.727(2) A (8)] and
carbon-chalcogen bond distances [1.801(8) (7); 1.917(1) A
(8)] increase with the size of the chalcogens. The C-E bond
distances in both compounds are closer to the C-E single-
bond distances [C-S: 1.81; C-Se: 1.94 A] than the C-E
double-bond distances [C-S: 1.61; C-Se: 1.74 A].39
18a
Me3)2}]2 The Pb-Pb distance is too long to consider the
presence of a bonding interaction. The average P-S bond
distance of 2.010 A is slightly longer than that in the neutral
ligand (1.944 A).32 This can be explained by the reduced
electron density of the P-S bond resulting from the S f Pb
donor bond.
The molecular structure of 6 is shown in Figure 4. Selected
bond distances (A) and angles (deg) of 6 are listed in Table 5.
Compound 6 consists of a Ge2S2 planar ring with the trans-
configuration of the two chloride atoms. The S-Ge-S0 angles
(96.25(4)ꢀ) are larger than the Ge-S-Ge angles (83.75(4)ꢀ).
All the thio sulfur atoms of the ligand remain uncoordina-
ted. The four-coordinated germanium adopts a tetrahedral
geometry. The average Ge-S bond distance of 2.218 A is
longer than that of 2.056(6) A in [Ge(S){N(SiMe3)C(Ph)-
C(SiMe3)(C5H4N-2)}Cl]33 and 2.063(3) A in [(Tbt)(Tip)-
GedS], but is within the typical Ge-S single-bond range
(2.17-2.25 A).34 The germanium carbon bond distance of
2.010(4) A and germanium chloride bond distance of 2.133(1)
A are shorter than those found in the starting compound 2. This
is expected for the higher oxidation state germanium(IV) center
in 6. The Ge-C bond distance of 2.010(4) A is similar to the
Ge(IV)-C bond distances of 1.94(1) A in [(MesGe)2S2Cl2],35
1.959(8) A in [GeH(C6H4-2-CH2NMe2)3],36 and 1.970(7) A in
[Ge(C6H5)3Cl].37 The Ge-Cl bond distance shows good agree-
Experimental Section
General Procedures. All manipulations were carried out under
an inert atmosphere of dinitrogen gas by standard Schlenk
techniques. Solvents were dried over and distilled from CaH2
(CH2Cl2) and/or Na (Et2O, THF, and toluene). GeCl2 dioxane,
SnCl2, S, and Se were purchased from Aldrich Chemical Co. and
used without further purification. CH2(PPh2dS)2, Sn{N(Si-
Me3)2}2, and Pb{N(SiMe3)2}2 were prepared according to the
literature procedures.7,40 The 1H, 13C, 31P, 119Sn, and 77Se NMR
spectra were recorded on Bruker DPX-300/DPX-400 or Varian
400 spectrometers. The NMR spectra were recorded in THF-d8,
and the chemical shifts δ are relative to SiMe4, 85% H3PO4,
SnMe4, and Me2Se for 1H, 13C, 31P, 19Sn, and 77Se, respectively.
[GeCl{CH(PPh2dS)2}] (2). A solution of 1 (3.36 g, 5.59
mmol) in Et2O (20 mL) was added slowly to a solution of
GeCl2 dioxane (1.28 g, 5.55 mmol) in Et2O (20 mL) at 0 ꢀC
3
with stirring. The resultant white suspension was raised to
ambient temperature and stirred for 18 h. Volatiles were re-
moved under reduced pressure. The residue was extracted with
CH2Cl2 and filtered. Addition of THF to the filtrate and
concentration gave 2 as colorless crystals. Yield: 2.17 g (70%).
Mp: 175.2-175.6 ꢀC (dec after melting). Anal. Found: C, 54.00;
H, 3.78. Calcd for C25H21ClGeP2S2: C, 54.04; H, 3.81. 1H NMR
(400 MHz, THF-d8): δ 3.83 (br t, 1H, CH), 7.29-7.40 (m, 12H,
(33) Leung, W.-P.; Chong, K.-H.; Wu, Y.-S.; So, C.-W.; Chan, H.-S.;
Mak, T. C. W. Eur. J. Inorg. Chem. 2006, 808.
(34) Tokitoh, N.; Matsumoto, T.; Manmaru, K.; Okazaki, R. J. Am.
Chem. Soc. 1993, 115, 8855.
(35) Puff, H.; Braun, K.; Franken, S.; Kok, T. R.; Schuh, W. J.
€
Organomet. Chem. 1987, 335, 167.
ꢀ
(36) Fajarı, L.; Julia, L.; Riera, J. J. Organomet. Chem. 1989, 363, 31.
´
ꢁ
ꢀ
ꢀ
(37) Breliere, C.; Carre, F.; Corriu, R. J. P.; Gerard, R.; Man,
M. W. C. Organometallics 1994, 13, 307.
(38) (a) Ding, Y.; Ma, Q.; Uson, I.; Roesky, H. W.; Noltemeyer, M.;
Schmidt, H.-G. J. Am. Chem. Soc. 2002, 124, 8542. (b) Ding, Y.; Ma, Q.;
(39) Pauling, L. The Nature of The Chemical Bond and The Structure
of Molecules and Crystals: An Introduction of Modern Structural Chem-
istry; Cornell University Press: Ithaca, NY, 1976; pp 221-264.
ꢀ
ꢀ
Roesky, H. W.; Uson, I.; Noltemeyer, M.; Schmidt, H.-G. Dalton Trans.
(40) Gynane, M. J. S.; Harris, D. H.; Lappert, M. F.; Power, P. P.;
ꢁ ꢁ
Riviere, P.; Riviere-Baudet, M. J. Chem. Soc., Dalton Trans. 1977, 2004.
2003, 1094.

818 Organometallics, Vol. 29, No. 4, 2010
Table 1. Crystallographic Data for Compounds 2, 4, and 5
Leung et al.
2
4
5
formula
fw
color
C
555.52
colorless
monoclinic
P21/n
16.213(3)
8.9053(14)
18.961(3)
90
113.280(3)
90
2514.8(7)
4
1.467
1.629
1128
25H21ClGeP2S2
C50H40P4S4Sn2 THF
3
C
1379.42
yellow
monoclinic
C2/c
19.971(4)
10.1578(18)
25.641(5)
90
94.569(5)
90
5185.0(17)
4
1.767
6.808
2672
50H40P4Pb2S4 THF
3
1202.42
yellow
cryst syst
space group
monoclinic
C2/c
19.962(3)
10.1888(16)
25.461(4)
90
94.424(3)
90
5163.0(14)
4
1.547
ꢀ
a (A)
b (A)
ꢀ
ꢀ
c (A)
R (deg)
β (deg)
γ (deg)
3
ꢀ
V (A )
Z
dcalcd (g cm-3
)
μ (mm-1
F(000)
)
1.292
2416
cryst size (mm)
2θ range (deg)
index range
0.30 ꢁ 0.20 ꢁ 0.20
1.40 to 28.02
-18 e h e 21,
-11 e k e 11,
-24 e l e 24
16 730
0.40 ꢁ 0.30 ꢁ 0.30
1.60 to 28.04
-26 e h e 26,
-13 e k e 13,
-27 e l e 33
17 047
0.50 ꢁ 0.40 ꢁ 0.40
1.59 to 25.00
-22 e h e 23,
-12 e k e 12,
-30 e l e 25
13 384
no. of rflns collected
no. of indep rflns
R1, wR2 (I > 2(σ)I)
R1, wR2 (all data)
goodness of fit, F2
no. of data/
6055
6212
4559
0.0639, 0.1833
0.1579, 0.2348
1.079
0.0373, 0.0850
0.0615, 0.0974
1.049
0.0456, 0.1189
0.0563, 0.1267
1.003
6055/0/280
6212/0/294
4559/0/294
restraints/params
largest diff peaks (e A
-3
ꢀ
)
0.739 to -0.517
0.930 to -0.324
3.117 to -2.297
˚
Table 3. Selected Bond Distances (A) and Angles (deg) for
Compounds 2 and 3
Table 2. Crystallographic Data for Compounds 6 and 8
6
8
[MCl{CH(PPh2dS)2}]
formula
fw
color
C
1463.57
colorless
monoclinic
C2/c
19.263(3)
13.8672(19)
28.132(4)
90
93.501(3)
90
7500.8(18)
4
1.296
1.167
3024
0.40 ꢁ 0.30 ꢁ 0.20
1.45 to 28.03
-25 e h e 20,
-18 e k e 18,
-30 e l e 37
50H42Cl2Ge2P4S6 4THF
3
C25H20P2PbS2Se
732.62
red
monoclinic
P21/n
13.3170(19)
10.7311(15)
18.023(3)
90
107.877(3)
90
2451.3(6)
4
1.985
8.680
1392
0.20 ꢁ 0.20 ꢁ 0.10
1.68 to 25.00
-15 e h e 14,
-12 e k e 12,
-18 e l e 21
13 056
M = Ge (2)
M = Sn (3)
cryst syst
space group
M(1)-C(1)
M(1)-Cl(1)
M(1)-S(1)
P(1)-C(1)
P(1)-S(1)
P(2)-C(1)
P(2)-S(2)
2.153(6)
2.288(2)
2.479(2)
1.786(6)
2.007(3)
1.803(6)
1.954(2)
2.374(2)
2.521(1)
2.636(1)
1.769(2)
2.017(1)
1.782(2)
1.959(1)
ꢀ
a (A)
ꢀ
b (A)
ꢀ
c (A)
R (deg)
β (deg)
γ (deg)
3
ꢀ
V (A )
Z
C(1)-M(1)-Cl(1)
C(1)-M(1)-S(1)
Cl(1)-M(1)-S(1)
C(1)-P(1)-S(1)
C(1)-P(2)-S(2)
P(1)-S(1)-M(1)
P(1)-C(1)-P(2)
P(1)-C(1)-M(1)
P(2)-C(1)-M(1)
94.6(2)
79.8(2)
86.35(6)
74.56(6)
93.29(3)
106.74(9)
112.05(9)
82.31(3)
122.0(1)
95.7(1)
dcalcd (g cm-3
)
97.31(8)
103.5(2)
111.7(2)
80.90(8)
119.8(4)
95.8(3)
μ (mm-1
F(000)
)
cryst size (mm)
2θ range (deg)
index range
107.2(3)
102.7(1)
no. of rflns collected 25 404
no. of indep rflns 9094
R1, wR2 (I > 2(σ)I) 0.0573, 0.1366
R1, wR2 (all data)
goodness of fit, F2
no. of data/
restraints/params
largest diff
ꢀ
peaks (e A
white suspension was raised to ambient temperature and stirred
for 18 h. Volatiles were removed under reduced pressure. The
residue was extracted with CH2Cl2 and filtered. The filtrate was
added with THF and concentrated to give 3 as colorless crystals.
Yield: 0.97 g (60%). Mp: 106.2 ꢀC (dec). Anal. Found: C, 49.66;
H, 3.51. Calcd for C25H21ClP2S2Sn: C, 49.91; H, 3.52. 1H NMR
(400 MHz, THF-d8): δ 4.20 (t, 1H, CH, JP-H = 13.5 Hz),
7.27-7.40 (m, 12H, Ph), 7.72-7.96 (m, 8H, Ph). 13C{1H} NMR
(100.6 MHz, THF-d8): δ 37.62 (t, PCP, JP-C = 47.3 Hz), 128.67
4312
0.0559, 0.1153
0.1539, 0.1635
0.992
0.1410, 0.1598
0.829
9094/0/379
4312/6/280
0.529 to -0.436
1.292 to -1.018
-3
)
Ph), 7.85-7.95 (m, 8H, Ph). 13C{1H} NMR (100.6 MHz,
THF-d8): δ 37.49 (t, PCP, JP-C = 46.8 Hz), 128.60, 128,66,
128.73, 128.80, 131.72, 132.44, 132,52, 132.57, 132.63, 132.71,
134.47 (d, J = 85.5 Hz) (Ph). 31P{1H} (121.5 MHz, THF-d8): δ
33.81, 39.95.
[SnCl{CH(PPh2dS)2}] (3). A solution of 1 (1.64 g, 2.73 mmol)
in Et2O (20 mL) was added slowly to the solution of SnCl2 (0.58
g, 3.06 mmol) in Et2O (20 mL) at 0 ꢀC with stirring. The resultant
(t, m-Ph, JP-C = 7.0 Hz), 131.72 (s, p-Ph), 132.58 (t, o-Ph,
3
2JP-C=5.0 Hz), 134.47 (d, ipso-Ph, 1JP-C=86.5 Hz). 31P{1H}
NMR (121.5 MHz, THF-d8): δ 33.82, 37.63. 119Sn{1H} NMR
(149.1 MHz, THF-d8): δ -129.58 (t, 2JSn-P=169 Hz).
[Sn{μ2-C(Ph2PdS)2}]2 (4). A mixture of CH2(PPh2dS)2 (1.19
g, 2.65 mmol) and Sn{N(SiMe3)2}2 (1.17 g, 2.66 mmol) in
toluene (20 mL) was stirred at room temperature for 3 days.
Volatiles were removed under reduced pressure. The residue was

Article
Organometallics, Vol. 29, No. 4, 2010 819
˚
Table 4. Selected Bond Distances (A) and Angles (deg) for
Compounds 4 and 5
[Sn{μ2-C(Ph2PdS)2}]2 (4)
Sn(1)-C(1A)
Sn(1)-C(1)
Sn(1)-S(1)
2.327(3)
2.514(3)
2.618(1)
P(1)-C(1)
P(1)-S(1)
P(2)-C(1)
P(2)-S(2)
1.741(3)
2.026(1)
1.758(3)
1.994(1)
C(1A)-Sn(1)-C(1)
C(1A)-Sn(1)-S(1)
C(1)-Sn(1)-S(1)
C(1)-P(1)-S(1)
C(1)-P(2)-S(2)
P(1)-S(1)-Sn(1)
91.2(1)
P(1)-C(1)-P(2)
125.4(2)
110.3(1)
102.9(1)
94.4(1)
128.9(1)
88.8(1)
92.73(7)
70.55(7)
103.6(1)
110.0(1)
84.95(4)
P(1)-C(1)-Sn(1A)
P(2)-C(1)-Sn(1A)
P(1)-C(1)-Sn(1)
P(2)-C(1)-Sn(1)
Sn(1A)-C(1)-Sn(1)
[Pb{μ2-C(Ph2PdS)2}]2 (5)
Pb(1)-C(1A)
Pb(1)-C(1)
Pb(1)-S(2)
Pb(1)-S(1A)
2.419(6)
2.593(7)
2.726(2)
3.085(2)
P(1)-C(1)
P(1)-S(1)
P(2)-C(1)
P(2)-S(2)
1.749(6)
2.000(2)
1.741(6)
2.020(3)
C(1A) -Pb(1)-C(1)
C(1A)-Pb(1)-S(2)
C(1)-Pb(1)-S(2)
C(1A)-Pb(1)-S(1A)
C(1)-Pb(1)-S(1A)
S(2)-Pb(1)-S(1A)
C(1)-P(1)-S(1)
91.8(2)
91.9(2)
68.1(1)
67.2(2)
135.1(1)
73.2(1)
111.2(2)
104.7(3)
P(1)-S(1)-Pb(1A)
P(2)-S(2)-Pb(1)
P(2)-C(1)-P(1)
P(2)-C(1)-Pb(1A)
P(1)-C(1)-Pb(1A)
P(2)-C(1)-Pb(1)
P(1)-C(1)-Pb(1)
Pb(1A)-C(1)-Pb(1)
76.9(1)
85.4(1)
126.8(4)
108.6(3)
102.3(3)
95.5(3)
128.1(3)
88.2(2)
Figure 2. Molecular structure of 4; 30% thermal ellipsoids are
shown.
C(1)-P(2)-S(2)
Figure 3. Molecular structure of 5; 30% thermal ellipsoids are
shown.
extracted with THF and filtered. After the yellow filtrate was
concentrated and allowed to stand for 3 days, bright yellow crys-
tals of 4 were obtained. Yield: 0.79 g (50%). Calcd for C50H40-
Figure 4. Molecular structure of 6; 30% thermal ellipsoids are
shown.
P4S4Sn2 THF: C, 53.94; H, 4.02. 1H NMR (300 MHz, THF-d8):
3
δ 7.28-7.41 (m, 24H, Ph), 7.89-7.97 (m, 16H, Ph). 13C{1H}
NMR (75.5 MHz, THF-d8): δ 128.68 (t, m-Ph, 3JP-C=6.3 Hz),
131.73 (p-Ph), 132.60 (t, o-Ph, JP-C = 5.4 Hz), 134.35 (d,
˚
Table 5. Selected Bond Distances (A) and Angles (deg) for
2
Compound 6a
1
ipso-Ph, JP-C =85.8 Hz). 31P{1H} NMR (121.5 MHz, THF-
d8): δ 32.01.
[GeCl{CH(PPh2dS)2}(μ-S)]2 4THF (6)
[Pb{μ2-C(Ph2PdS)2}]2 (5). A mixture of CH2(PPh2dS)2
(1.30 g, 2.90 mmol) and Pb{N(SiMe3)2}2 (1.54 g, 2.91 mmol)
in toluene (20 mL) was stirred at room temperature for 3 days.
Volatiles were removed under reduced pressure, and the resi-
due was extracted with THF. After filtration and concen-
tration of the filtrate, compound 5 was obtained as yellow
crystals. Yield: 1.28 g (64%). Mp: 155 ꢀC (dec). Anal. Found:
3
Ge(1)-C(1)
Ge(1)-Cl(1)
Ge(1)-S(3)
Ge(1)-S(3A)
2.010(4)
2.133(1)
2.209(1)
2.226(1)
P(1)-C(1)
P(1)-S(1)
P(2)-C(1)
P(2)-S(2)
1.851(4)
1.934(2)
1.845(4)
1.939(2)
C(1)-Ge(1)-Cl(1)
C(1)-Ge(1)-S(3)
Cl(1)-Ge(1)-S(3)
C(1)-Ge(1)-S(3A)
Cl(1)-Ge(1)-S(3A)
S(3)-Ge(1)-S(3A)
112.1(1)
118.0(1)
108.5(1)
111.9(1)
108.9(1)
96.25(4)
Ge(1)-S(3)-Ge(1A)
C(1)-P(1)-S(1)
C(1)-P(2)-S(2)
P(2)-C(1)-P(1)
P(2)-C(1)-Ge(1)
P(1)-C(1)-Ge(1)
83.75(4)
115.8(2)
110.9(2)
117.2(2)
106.7(2)
113.3(2)
C, 46.49; H, 3.38. Calcd for C50H40P4Pb2S4 1/2THF: C, 46.49;
3
1
H, 3.30. H NMR (300 MHz, THF-d8): δ 7.10-7.41 (m, 24H,
Ph), 7.69-7.97 (m, 16H, Ph). 13C{1H} NMR (100.6 MHz,
THF-d8): δ 128.45-128.72 (m, m-Ph), 130.92 (p-Ph), 131.71
(p-Ph), 131.90 (t, o-Ph, 2JP-C=5.5 Hz), 132.58 (t, o-Ph, 2JP-C
=
a Symmetry transformations used to generate equivalent atoms:
-xþ3/2, -yþ3/2, -zþ2.
5.4 Hz), 134.48 (d, ipso-Ph, 1JP-C=85.9 Hz), 138.57 (d, ipso-Ph,

820 Organometallics, Vol. 29, No. 4, 2010
Leung et al.
˚
Table 6. Selected Bond Distances (A) and Angles (deg) for
Compounds 7 and 8
[PbE{C(PPh2dS)2}]
E = S (7)
E = Se (8)
Pb(1)-E
2.632(2)
2.736(3)
2.830(2)
1.748(8)
2.031(3)
1.725(8)
2.045(3)
1.801(8)
2.727(2)
2.750(4)
2.813(4)
1.749(1)
2.019(6)
1.741(1)
2.060(6)
1.917(1)
Pb(1)-S(2)
Pb(1)-S(1)
P(1)-C(1)
P(1)-S(1)
P(2)-C(1)
P(2)-S(2)
E-C(1)
E-Pb(1)-S(2)
E-Pb(1)-S(1)
S(2)-Pb(1)-S(1)
C(1)-P(1)-S(1)
C(1)-P(2)-S(2)
P(1)-S(1)-Pb(1)
P(2)-S(2)-Pb(1)
C(1)-E-Pb(1)
P(2)-C(1)-P(1)
P(2)-C(1)-E
83.7 (1)
82.6(1)
91.4(1)
114.6(3)
115.6(3)
96.2(1)
96.7(1)
96.0(3)
122.6(5)
108.9(4)
108.0(4)
83.0(1)
84.6(1)
93.1(1)
116.3(5)
115.7(5)
96.9(2)
97.6(2)
92.1(4)
121.8(7)
107.5(7)
109.8(7)
Figure 5. Molecular structure of 8; 30% thermal ellipsoids are
shown.
P(1)-C(1)-E
selenium (0.24 g, 3.05 mmol) in toluene (20 mL) at 0 ꢀC with
stirring in the absence of light. The resultant dark brown
suspension was raised to ambient temperature and stirred for
2 days. Volatiles were removed under reduced pressure, and the
residue was extracted with THF. The insoluble precipitate was
filtered off. The filtrate was concentrated to give red crystals of
8. Yield: 0.48 g (25%). Mp: 150.6-151.1 ꢀC (dec). Anal. Found:
C, 41.17; H, 2.75. Calcd for C25H20P2PbS2Se: C, 40.98; H, 2.75.
1H NMR (400 MHz, THF-d8): δ 7.30-7.40 (m, 12H, Ph),
7.90-7.96 (m, 8H, Ph). 13C{1H} NMR (75.5 MHz, THF-d8):
δ 128.59, 128.68, 128.76, 131.72, 132.52, 132.60, 132.67, 134.35,
135.49. 31P{1H}NMR (162.0 MHz, THF-d8): δ 31.86, 59.39.
77Se NMR (THF-d8): δ 893.34.
Figure 6. View of the boat conformation of the six-membered
PbS2P2C ring in compounds 7 and 8.
1JP-C=89.6 Hz). 31P{1H} NMR (121.5 MHz, THF-d8): δ 33.83,
35.72.
[GeCl{CH(PPh2dS)2}(μ-S)]2 (6). A solution of 2 (0.50 g,
0.90 mmol) in THF (20 mL) was added to a solution of sulfur
(0.04 g, 1.25 mmol) in THF (10 mL) at 0 ꢀC with stirring. The
resultant pale yellow suspension was raised to ambient tempera-
ture and stirred for 48 h. It was then filtered and concentrated,
yielding colorless crystals of 6. Yield: 0.14 g (21%). Mp: 139.2 ꢀC
(dec). Anal. Found: C, 52.47; H, 4.43. Calcd for C50H42-
X-ray Crystallography. Single crystals were sealed in Linde-
mann glass capillaries under nitrogen. X-ray data of 2-8 were
€
collected on a Bruker SMART CCD diffractrometer with a Mo
KR sealed tube, in ω scan mode with an increment of 0.3ꢀ.
Crystal data of 2, 4, 5, 6 and 8 are summarized in Tables 1 and 2.
The structures were solved by direct phase determination using
the computer program SHELXL-9741 and refined by full-matrix
least-squares with anisotropic thermal parameters for the non-
hydrogen atoms. Hydrogen atoms were introduced in their
idealized positions and included in structure factor calculations
with assigned isotropic temperature factor calculations. Full
details of the crystallographic analysis are given in the Support-
ing Information.
Cl2Ge2P4S6 2THF: C, 52.79; H, 4.43. 1H NMR (300 MHz,
3
THF-d8): δ 1.69 (4H, THF), 3.54 (4H, THF), 4.17 (t, 2H, CH,
JP-H =13.5 Hz), 6.99-7.18 (m, 4H, Ph), 7.26-7.54 (m, 20H,
Ph), 7.64-7.93 (m, 12H, Ph), 7.96-8.04 (m, 4H, Ph). 13C{1H}
NMR (100.6 MHz, THF-d8): δ 26.38 (THF), 68.22 (THF),
128.24-129.19 (m, Ph), 131.71(Ph), 132.44-133.11 (m, Ph),
1
134.48 (d, ipso-Ph, JP-C = 85.6 Hz). 31P{1H} (162.0 MHz,
THF-d8): δ 36.78.
[PbS{C(PPh2dS)2}] (7). A solution of 5 (1.27 g, 0.92 mmol) in
toluene (20 mL) was added slowly to a solution of powdered
sulfur (0.06 g, 1.87 mmol) in toluene (20 mL) at 0 ꢀC with
stirring. The resultant red suspension was raised to ambient
temperature and stirred for 18 h. Volatiles were removed under
reduced pressure, and the residue was extracted with THF. After
filtration and concentration of the filtrate, compound 7 was
obtained as red crystals. Yield: 0.19 g (14%). Mp: 129.8 ꢀC (dec).
Acknowledgment. This work was supported by the
Chinese University of Hong Kong Direct Grant
(Project No. 2060353). We also thank Professor S. L.
Lam’s group for carrying out the 31P-31P EXSY NMR
experiment of compound 5.
Supporting Information Available: Details about the X-ray
crystal structures, including ORTEP diagrams and tables of
crystal data and structure refinement, atomic coordinates, bond
lengths and angles, and anisotropic displacement parameters for
2, 4, 5, 6, and 8. This material is available free of charge via the
Internet at http://pubs.acs.org.
Anal. Found: C, 46.03; H, 3.76. Calcd for C25H20P2PbS3 THF:
3
C, 45.96; H, 3.72. 1H NMR (400 MHz, THF-d8): δ 1.69 (s,
2.5H, 0.75 THF), 3.54 (s, 2.5H, 0.75 THF), 7.19-7.46 (m, 12H,
Ph), 7.87-7.92 (m, 8H, Ph). 13C{1H} NMR (75.5 MHz, THF-
d8): δ 26.39 (THF), 68.22 (THF), 128.67, 130.87, 131.72, 132.52,
132.60, 132.67, 134.67, 135.48 (Ph). 31P{1H}NMR (162.0 MHz,
THF-d8): δ 31.87, 57.73.
(41) Sheldrick, G. M. SHELX-97, Program for Crystal Structure
€
[PbSe{C(PPh2dS)2}] (8). A solution of 5 (1.82 g, 1.32 mmol)
in toluene (20 mL) was added slowly to a solution of powdered
€
Refinement from Diffraction Data; University of Gottingen: Gottingen,
Germany, 1997.