Synthesis and structure of magnesium and group 13 metal bis(thiophosphinoyl)methanediide complexes

Article abstract of DOI:10.1021/om100019c

Metalations of bis(diphenylthiophosphinoyl)methane, CH₂(PPh ₂-S)₂, with equimolar BuⁿLi or Bu ⁿ₂Mg in THF afforded [Li{(S-PPh₂) ₂CH}(THF)(Et₂O)] (1) and [MgC(PPh₂-S) ₂(THF)]₂ (2), respectively. Compound 1 with a group 13 metal chloride MCl₃ (M = Al, Ga, In) gave the methanediide complex [MCl{C(PPh₂-S)₂}]₂ (M = Al (3), Ga (4), In (5)). Compounds 3?5 are believed to be formed by ligand transfer reaction followed by dehydrochlorination. X-ray structures of 1?5 have been determined. It was found that the magnesium complex 2 has a similar structure to the group 13 metal analogues 3?5.

Full text of DOI:10.1021/om100019c

1622 Organometallics 2010, 29, 1622–1628
DOI: 10.1021/om100019c
Synthesis and Structure of Magnesium and Group 13 Metal
Bis(thiophosphinoyl)methanediide Complexes
Wing-Por Leung,* Chi-Ling Wan, and Thomas C. W. Mak
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong,
People’s Republic of China
Received January 7, 2010
Metalations of bis(diphenylthiophosphinoyl)methane, CH2(PPh2dS)2, with equimolar BunLi or
Bun Mg in THF afforded [Li{(SdPPh2)2CH}(THF)(Et2O)] (1) and [MgC(PPh2dS)2(THF)]2 (2),
2
respectively. Compound 1 with a group 13 metal chloride MCl3 (M = Al, Ga, In) gave the
methanediide complex [MCl{C(PPh2dS)2}]2 (M = Al (3), Ga (4), In (5)). Compounds 3-5 are
believed to be formed by ligand transfer reaction followed by dehydrochlorination. X-ray structures
of 1-5 have been determined. It was found that the magnesium complex 2 has a similar structure to
the group 13 metal analogues 3-5.
Introduction
rapidly. Numerous main group, transition metal, and rare
earth metal complexes of this kind were synthesized.4-6
However, only a few examples of group 13 methanediide
complexes are known. Cavell and co-workers have reported
the first example of bis(iminophosphorano)methanediide
complexes [(AlR2)2{μ2-C(Ph2PdNSiMe3)2-κ2N,N0}] (R = Me,
Bu).7,8 The aluminum methanediide complex [(AlBu)2-
Ph2P(S)SPPh2(S)2(AlBu)2] has a related ligand.9 These
compounds are bridging bi- and tetrametallic complexes,
respectively. Moreover, the gallium and indium methane-
diide complexes were unknown. Herein, we report the
synthesis of a series of metal (M = Al, Ga, In, and Mg) bis-
(thiophosphinoyl)methanediide complexes, in which there is
direct interaction between the metal and the methanediide
carbon.
The chemistry of group 13 metal organometallic complexes,
especially the organoaluminium compounds, has been widely
explored on account of their uses in polymerization catalysis.
Various ligands containing N-donor sites have been used to
stabilize these metal complexes.1 For example, the imino and
sulfur derivatives of bis(diphenylphosphino)methane have
been studied extensively in the past few decades. Dilithium
methanediide complexes [Li2C(PPh2dX)2] (X = NSiMe3, S)
have been prepared and structurally characterized.2,3 The
coordination chemistry of bis(iminophosphorano)- and bis-
(thiophosphinoyl)methanediide complexes has developed
*Corresponding author. E-mail: kevinleung@cuhk.edu.hk.
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C.; Junk, P. C.; Platts, J. A.; Stasch, A. J. Am. Chem. Soc. 2006, 128, 2206.
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r
pubs.acs.org/Organometallics
Published on Web 02/26/2010
2010 American Chemical Society

Article
Organometallics, Vol. 29, No. 7, 2010 1623
Scheme 1
Scheme 2
Figure 1. Molecular structure of 1 with 30% thermal ellipsoids.
(M = Al (3a), Ga (4a), In (5a)) formed underwent further de-
hydrochlorination to give compounds 3-5. The mono-
lithium complex 1 acts both as a ligand transfer reagent
and as a base for dehydrochlorination. Similar dehydro-
chlorination has been reported in the synthesis of bisgerma-
vinylidene from the reaction of GeCl2 dioxane with [Li{CH-
(PPh2dNSiMe3)2}(THF)].4a Until now, only the aluminum
methandiide complex [{(Ph2PdNSiMe3)(Ph2PdS)}CAlMe]2
with one Al-C bond has been synthesized and structurally
characterized.11
Spectroscopic Properties. Compounds 1 and 3-5 were
isolated as colorless crystalline solids, while compound 2 is
a yellow crystalline solid. Compound 1 is extremely air and
moisture sensitive. The 1H NMR and 13C NMR spectra of 1
displayed signals assignable to the bis(thiophosphinoyl)-
methanide ligand, together with solvated THF and Et2O
molecules. The 1H NMR spectrum of 1 showed a triplet at
δ 2.23 ppm (JP-H = 1.8 Hz) for the methanide proton on the
P-C-P backbone with coupling to two equivalent phos-
phorus nuclei. These indicate considerable delocalization
throughout the SPCPS backbone of the ligand. This is also
consistent with the 31P NMR, which showed one singlet at
δ 37.61 ppm. The 13C NMR spectrum of 1 is normal.
Compound 2 is an extremely air-sensitive solid. Although
no signal was observed for the carbenic carbon in the 13C
NMR spectrum of 2, the absence of signals assignable to the
Results and Discussion
Synthesis of Lithium and Magnesium Bis(thiophosphinoyl)
Complexes. The acidity of the methylene protons in bis-
(diphenylthiophosphinoyl)methane, CH2(PPh2dS)2, is en-
hanced by the thiophosphinoyl groups and therefore can be
deprotonated by bases. Reaction of CH2(PPh2dS)2 with one
equivalent of BunLi in THF at 0 °C afforded the mono-
lithium complex [Li{(SdPPh2)2CH}(THF)(Et2O)] (1), while
that with equimolar Bun Mg in THF at 60 °C afforded the
2
magnesium methanediide complex [MgC(PPh2dS)2(THF)]2
(2) (Scheme 1). Double deprotonation of related bis(phos-
phorus)-stabilized compounds is usually done by lithium
alkyl.2,3,10 Magnesium methanediide complexes [{(Ph2Pd
NSiMe3)(Ph2PdE)}CMg]2 (E=S, NSiMe3) containing mag-
nesium atoms that bridge the methandiide carbon have been
reported recently.11 To our knowledge, compound 2 is the
first example of a methandiide carbon bonded to one mag-
nesium atom.
1
methylene protons in compound 2 was confirmed by H
NMR spectroscopy. The 31P NMR spectrum of 2 displays
two singlets at δ 14.05 and 34.96 ppm, which does not
correspond to the solid-state X-ray structure. The variable-
temperature 31P NMR of 2 in d8-THF has been carried out in
the range from 60 to -60 °C. The two peaks did not coalesce
at temperature up to 60 °C. The 31P-31P EXSY NMR
spectrum of 2 in d8-THF has also been recorded. There
were no cross-peaks in the spectrum; therefore no exchange
between the two phosphorus atoms was present. We propose
that the phosphorus atoms within the molecule might have
two different environments in solution.
Synthesis of Group 13 Metal Bis(thiophosphinoyl) Com-
plexes. Group 13 bis(thiophosphinoyl)methanediide metal
chlorides [MCl{C(PPh2dS)2}]2 (M = Al (3), Ga (4), In (5))
have been synthesized from the reaction of MCl3 with two
equivalents of 1 in Et2O at 0 °C (Scheme 2). On the basis of
the structures and spectroscopic data of products obtained,
it is proposed that the intermediate [MCl2{C(PPh2dS)2}]
1
The H and 13C NMR spectra of 3-5 showed a similar
(10) Chen, J.-H.; Guo, J.; Li, Y.; So, C.-W. Organometallics 2009, 28,
4617.
(11) Guo, J.; Lee, J.-S.; Foo, M.-C.; Lau, K.-C.; Xi, H.-W.; Lim,
pattern and displayed one set of signals due to the ligand.
There is one sharp singlet [δ 32.24 (3); δ 31.86 (4); δ 31.87
ppm (5)] in all of their 31P NMR spectra. This indicates that
H. W.; So, C.-W. Organometallics 2010, 29, 939.

1624 Organometallics, Vol. 29, No. 7, 2010
Leung et al.
˚
Table 2. Selected Bond Distances (A) and Angles (deg) for
Compounds 1 and 2
Table 1. Crystallographic Data for Compounds 1 and 2
1
2
formula
C
33H39-
LiO2P2S2
C58H56Mg2-
O2P4S4 2THF
1229.98
yellow
monoclinic
P21/c
10.420(4)
13.181(5)
23.464(9)
90
96.986
90
3199(2)
2
1.277
0.315
1296
[Li{(SdPPh2)2CH}(THF)(Et2O)] (1)
3
Li(1)-O(1)
Li(1)-O(2)
Li(1)-S(1)
Li(1)-S(2)
1.941(1)
1.960(1)
2.422(1)
2.421(1)
P(1)-C(13)
P(1)-S(1)
P(2)-C(13)
P(2)-S(2)
1.712(4)
1.993(2)
1.711(4)
1.993(2)
fw
color
600.64
colorless
triclinic
P1
cryst syst
space group
ꢀ
˚
a (A)
10.4369(18)
10.6649(18)
17.073(3)
81.831(4)
73.596(3)
69.205(3)
1702.4(5)
2
O(1)-Li(1)-O(2)
O(1)-Li(1)-S(1)
O(1)-Li(1)-S(2)
O(2)-Li(1)-S(1)
O(2)-Li(1)-S(2)
S(2)-Li(1)-S(1)
101.9(5)
117.3(5)
104.7(5)
108.5(5)
116.5(5)
108.1(4)
C(13)-P(1)-S(1)
C(13)-P(2)-S(2)
P(1)-S(1)-Li(1)
P(2)-S(2)-Li(1)
P(2)-C(13)-P(1)
118.6(2)
117.1(2)
102.9(2)
106.6(3)
126.8(3)
ꢀ
˚
b (A)
ꢀ
˚
c (A)
R (deg)
β (deg)
γ (deg)
3
ꢀ
˚
V (A )
Z
[MgC(PPh2dS)2(THF)]2 2THF (2)
3
dcalcd (g cm-3
)
1.172
0.277
636
μ (mm-1
F(000)
)
Mg(1)-O(1)
Mg(1)-C(1A)
Mg(1)-S(1)
Mg(1)-S(2)
2.061(4)
2.156(5)
2.455(2)
2.459(2)
P(1)-C(1)
P(1)-S(1)
P(2)-C(1)
P(2)-S(2)
1.708(5)
2.026(2)
1.702(5)
2.039(2)
cryst size (mm)
2θ range (deg)
index ranges
0.50 ꢀ 0.40 ꢀ 0.30 0.40 ꢀ 0.30 ꢀ 0.20
1.24 to 25.00
-12 e h e 9,
-12 e k e 12,
-20 e l e 20
9291
1.75 to 28.05
-13 e h e 13,
-16 e k e 17,
-26 e l e 30
21 358
O(1)-Mg(1)-C(1A)
O(1)-Mg(1)-S(1)
C(1A)-Mg(1)-S(1)
O(1)-Mg(1)-S(2)
C(1A)-Mg(1)-S(2)
S(1)-Mg(1)-S(2)
114.0 (2)
95.0(1)
117.7(1)
95.0(1)
121.7(1)
108.0(1)
C(1)-P(1)-S(1)
118.3(2)
117.5(2)
96.7(1)
C(1)-P(2)-S(2)
P(1)-S(1)-Mg(1)
P(2)-S(2)-Mg(1)
P(2)-C(1)-P(1)
P(2)-C(1)-Mg(1A)
P(1)-C(1)-Mg(1A)
no. of rflns collected
no. of indep rflns
R1, wR2 (I >2(σ)I)
R1, wR2 (all data)
goodness of fit, F2
97.0(1)
5975
7736
119.0(3)
115.0(2)
115.4(2)
0.0785, 0.2216
0.1015, 0.2406
1.075
0.0666, 0.1645
0.1906, 0.2355
1.012
no. of data/restraints/params 5975/9/361
)
7736/10/361
0.468 to -0.302
14
˚
˚
-3
ꢀ
˚
largest diff peaks (e A
(2.460(8) A) and HC(Ph2PdNSiMe3)2MgI(THF) (2.573(6) A)
as well as those of magnesium methandiide complexes
[{(Ph2PdNSiMe3)(Ph2PdE)}CMg]2 (E = S (average 2.241);
0.739 to -0.426
the phosphorus atoms in these compounds are in the same
environment.
X-ray Structures. The molecular structure of 1 is shown in
11
˚
NSiMe3 (average 2.235 A))]. This value also shows good
˚
agreement with the calculated Mg-C bond (2.08-2.10 A)
˚
of MgdCH2.15 The relatively short P-C bond length of
1.705 A suggests that the thiophosphinoyl arms help to
Figure 1. Selected bond distances (A) and angles (deg) of 1
are listed in Table 2. Compound 1 is a monomeric lithium
complex. The Li(1) coordinates to the ligand with S,S0-
chelation to form a six-membered ring. The lithium is bonded
to a THF and a Et2O molecule to adopt a tetrahedral geometry.
It is rare that a lithium atom is coordinated to two different ether
molecules in a coordinated compound. The Li-S bond dis-
˚
stabilize the electron density on the carbon center.
Compounds 3-5 are isostructural, and their molecular
structures are illustrated in Figures 3-5. Selected bond
˚
distances (A) and angles (deg) of 3-5 are shown in
Table 4. All of 3-5 are dimeric species bearing structural
resemblance to [MgC(PPh2dS)2(THF)]2 (2). The metal cen-
ter is bonded to the chlorine atom instead of a THF molecule,
a methanediide carbon, and two thio sulfur atoms from an
adjacent ligand, leading to a tetrahedral environment. It is
noteworthy that compounds 3-5 possess an inversion center
i, so that half of the structures is centrosymmetric to the other
half. The sum of angles of 351.9°, 350.4°, and 352.4° in 3, 4,
and 5 around the C(1) atom is indicative of a sp2 carbon.
The average metal-sulfur bond and metal-chloride bond
distances increase down the group [M-S: 2.286 (3), 2.298 (4),
˚
tances of 2.422(1) and 2.421(1) A in 1are comparable to those of
12
2.474(8) and 2.473(8) A in [Li{(SdPPh2)2N}(THF)2]. The
˚
˚
P-S bond distances [1.993(2), 1.993(2) A] and the P-C bond
˚
distances [1.712(4), 1.711(4) A] in 1 are different from those of
CH2(PPh2dS)2 [P-S: 1.944 A; P-C: 1.829 A].13 These suggest
that charge delocalization within the SPCPS skeleton is present.
The P(2)-C(13)-P(1) angle of 126.8(3)° is larger than that of
118.4(2)° in CH2(PPh2dS)2.
˚
˚
The molecular structure of 2 is shown in Figure 2. Selected
˚
bond distances (A) and angles (deg) of 2 are listed in Table 2.
Compound 2 is a dimeric species with two magnesium
methanediide molecules bonded side-by-side via the sulfur
atoms in a head-to-tail fashion. The magnesium metal center
is bonded to the methanediide carbon atom, two thio sulfur
atoms from an adjacent ligand, and a THF molecule to give a
tetrahedral geometry. The angles at the three coordinated
˚
2.480 (5); M-Cl: 2.169(1) (3), 2.219(2) (4), 2.410(1) A (5)].
There is also an interesting trend in the M-C contact
lengths. The Al-C bond distance [1.975(2) A] and Ga-C
bond distance [1.972(4) A] are very close to each other, while
the In-C bond distance [2.173(3) A] is much longer. These
˚
˚
˚
M-C bond distances are in between the M-C single and
double bond length values [M-C: 2.032 (Al), 2.032 (Ga),
2.212 (In); MdC: 1.927 (Al), 1.927 (Ga), 2.107 A (In)].
methanediide carbon atoms [119.0(3)°, 115.4(2)°, 115.0(2)°;
P
bond angles = 349.4°] support the existence of a sp2-
hybridized carbon. The Mg(1)-C(1A) bond distance
16
˚
In addition, they are relatively shorter than the similar
M-C bond in N-heterocyclic carbene complexes [Al-C:
˚
(2.156(5) A) is significantly shorter than the reported Mg-C
single bond distances of [HC(Ph2PdNSiMe3)2Mg(μ-Cl)]2
(14) Wei, P.; Stephan, D. W. Organometallics 2003, 22, 601.
(15) Bare, W. D.; Citra, A.; Trindle, C.; Andrews, L. Inorg. Chem.
2000, 39, 1204.
(16) Pauling, L. The Nature of The Chemical Bond and The Structure
of Molecules and Crystals: An Introduction of Modern Structural Chemistry;
Cornell University Press: Ithaca, NY, 1976; pp 221-264.
(12) Chem, F.; Kapon, M.; Woollins, D.; Eisen, M. S. Organo-
metallics 2009, 28, 2391.
(13) 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. 7, 2010 1625
Figure 2. Molecular structure of 2 with 30% thermal ellipsoids.
Figure 3. Molecular structure of 3 with 30% thermal ellipsoids.
17
˚
˚
2.031-2.124, Ga-C: 2.071-2.131, In-C: 2.200-2.267 A].
single bond distance of 2.119
A
in [(AlMe2)2{μ2-
4
7
0
0
˚
Also, the Al-C bond distance is shorter than the Al-C
C(Ph2PdNSiMe3)2-κ C,C ,N,N }] and that of 2.097(4) A
in [Al(Me2)C(PPh2dS)(PPh2dSfAlMe3)].18 It is found that
the Al-C bond distance of 5 is very similar to that of
(17) (a) Arguengo, A. J.III; Dias, H. V. R.; Calabrese, J. C.;
Davidson, F. J. Am. Chem. Soc. 1992, 114, 9724. (b) Li, X.-W.; Su, J.;
Robinson, G. H. Chem. Commun. 1996, 2683. (c) Francis, M. D.; Hibbs, D. E.;
Hursthouse, M. B.; Jones, C.; Smithies, N. A. J. Chem. Soc., Dalton Trans. 1998,
3249. (d) Abernethy, C. D.; Cole, M. L.; Jones, C. Organometallics 2000, 29,
4852. (e) Baker, R. J.; Farley, R. D.; Jones, C.; Kloth, M.; Murphy, D. M. Chem.
Commun. 2002, 1196. (f) Shih, W.-C.; Wang, C.-H.; Chang, Y.-T.; Yap, G. P. A.;
Ong, T.-G. Organometallics 2009, 28, 1060. (g) Ghadwal, R. S.; Roesky, H. W.;
Herbst-Irmer, R.; Jones, P. G. Z. Anorg. Allg. Chem. 2009, 635, 431.
11
˚
[{(Ph2PdNSiMe3)(Ph2PdS)}CAlMe]2 (1.976(1) A).
˚
In compound 3, the average Al-S bond distance of 2.286 A
is comparatively shorter than those in [{Me2Si(μ-NBut)2Pd
(18) Self, M. F.; Lee, B.; Sangokoya, S. A.; Pennington, W. T.;
Robinson, G. H. Polyhedron 1990, 9, 313.

1626 Organometallics, Vol. 29, No. 7, 2010
Leung et al.
Figure 5. Molecular structure of 5 with 30% thermal ellipsoids.
In these three compounds, the P-S bonds [2.062 (3), 2.053
Figure 4. Molecular structure of 4 with 30% thermal ellipsoids.
S(NPh)-κN-κS}AlMe2] (2.352(1) A),19 [Al(Me2)C(PPh2dS)-
˚
18
(PPh2dSfAlMe3)] (2.388(2), 2.460(2) A), and [(AlMe3)-
˚
˚
(4), 2.058 A (5)] are lengthened and the P-C bonds [1.723 (3),
1.715 (4), 1.721 A (5)] are shortened relative to the free ligand
18
˚
(SdPPh2CH2CH2PPh2dS)(AlMe3)] (2.506(3) A). The Al-
Cl bond distance of 2.169(1) A is comparable to those of
˚
˚
[(SdPPh2)2CH2]; this is consistent with π-delocalization
around the MS2P2C ring.
1m
2.126 A in [{HC(CMeNAr)2}AlCl2], 2.152(1) A in [{(Me3-
˚
˚
SiNCH2CH2)2NMe}AlCl],20 and 2.149 A in [{HC(Ph2Pd
˚
NMes)2}AlCl2].21
Conclusion
˚
The average Ga-S bond distance of 2.298 A in 4 is similar
to that of 2.273 A in [GaCl2{N(Ph2PdS)2}] but shorter
22
˚
To summarize, lithium and magnesium thiophosphinoyl
complexes were readily prepared from CH2(PPh2dS)2. The
monolithium salt is a versatile precursor to access the first
series of group 13 bis(thiophosphinoyl)methanediide com-
plexes. There is an unusual direct interaction between the
metal and methanediide carbon in the magnesium and group
13 metal complexes. Reactivity studies that explore this
interaction are being pursued in our laboratory.
23
than those of 2.398 A in [GaMe2{N(Ph2PdS)2}] and
˚
23
2.3886(9) A in [GaMe2{(SdPPh2)N(C9H10NCdS}]. The
˚
˚
Ga-Cl bond (2.219(2) A) has a similar bond length to the
corresponding bond in [GaCl2{N(Ph2PdS)2}] (2.169 A),
˚
[{CH(Ph2PdNSiMe3)2}GaCl2] (2.200 A),
22
˚
24
and [{HC-
1m
˚
(CMeNAr)2}GaCl2] (2.223 A).
˚
In the case of 5, the average In-S bond distance of 2.481 A
agrees with that of 2.485 A in [InI2{N(Ph2PdS)2}] but is
25
˚
shorter than those in [InCl{N(Pr 2PdS)2}2] (2.5715 A)26 and
i
˚
Experimental Section
[κ -N,N ,S-{4,5-P(S)Ph2}2(μ-tz)]InMe2]2] (2.780(1) A).27 It is
believed that the higher indium coordination number in the
latter two compounds lengthens the In-S bond. The In-
3
0
˚
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 Na (Et2O, toluene, and THF). CH2(PPh2dS)2
was prepared according to the literature procedures.3 BunLi
˚
Cl bond distance of 2.410(1) A is comparable to those of
i
2.410(2) A in [InCl{N(Pr 2PdS)2}2] and 2.396 A in
26
˚
˚
[{HC(CMeNAr)2}InCl2].1m
(1.6 M in hexane), Bun Mg (1.0 M in heptane), AlCl3, GaCl3,
2
and InCl3 were purchased from Aldrich Chemical Co. and used
without further purification. The 1H, 13C, and 31P NMR spectra
(19) Haagenson, D. C.; Moser, D. F.; Stahl, L. Inorg. Chem. 2002, 41,
1245.
€
€
were recorded on Bruker DPX-300 or Bruker DPX-400 spectro-
meters. The NMR spectra were recorded in C6D6 and THF-d8,
and the chemical shifts δ are relative to SiMe4 and 85% H3PO4
for 1H, 13C, and 31P, respectively.
ꢀ
(20) Emig, N.; Nguyen, H.; Krautscheid, H.; Reau, R.; Cazaux, J.-B.;
Bertrand, G. Organometallics 1998, 17, 3599.
(21) Hill, M. S.; Hitchcock, P. B.; Karagouni, S. M. A. J. Organomet.
Chem. 2004, 689, 722.
[Li{(SdPPh2)2CH}(THF)(Et2O)] (1). BunLi (4.40 mL, 7.04
mmol, 1.6 M solution in hexane) was added slowly to a solution
of CH2(PPh2dS)2 (3.12 g, 6.96 mmol) in THF (50 mL) at 0 °C.
The temperature of the reaction mixture was raised to ambient
temperature and stirred for 15 h. Volatiles were removed under
reduced pressure, and the residue was extracted with Et2O. After
filtration and concentration of filtrate, 1 was obtained as color-
less crystals. Yield: 3.48 g (83%). Mp: 169.2-172.1 °C. Anal.
Found: C, 65.36; H, 6.54. Calcd for C33H39LiO2P2S2: C, 65.99;
H, 6.54. 1H NMR (400 MHz, C6D6): δ 1.05 (t, 3H, Et2O, J =
ꢀ
(22) Munoz-Hernandez, M.-A.; Montiel-Palma, V.; Huitron-Rattinger,
~
E.; Cortes-Llamas, S.; Tiempos-Flores, N.; Grevy, J.-M.; Silvestru, C.;
ꢀ
ꢀ
ꢀ
Power, P. P. Dalton Trans. 2005, 193.
ꢀ
(23) Montiel-Palma, V.; Huitron-Rattinger, E.; Cortes-Llamas, S.;
Munoz-Hernandez, M.-A.; Garcıa-Montalvo, V.; Lopez- Honorato, E.;
ꢀ
ꢀ
~
ꢀ
ꢀ
Silvestru, C. Eur. J. Inorg. Chem. 2004, 3743.
(24) Ong, C. M.; McKarns, P.; Stephan, D. W. Organometallics 1999,
18, 4197.
(25) Abbati, G. L.; Aragoni, M. C.; Arca, M.; Devillanova, F. A.;
Fabretti, A. C.; Garau, A.; Isaia, F.; Lippolis, V.; Verani, G. Dalton
Trans. 2003, 1515.
(26) Darwin, K.; Gilby, L. M.; Hodge, P. R.; Piggott, B. Polyhedron
1999, 18, 3729.
(27) Moya-Cabrera, M.; Jancik, V.; Castro, R. A.; Herbst-Irmer, R.;
Roesky, H. W. Inorg. Chem. 2006, 45, 5167.
7.0 Hz), 1.17-1.20 (m, 4H, THF), 2.23 (t, 1H, CH, JP-H
1.8 Hz), 3.19-3.25 (q, 2H, Et2O, J = 7.0 Hz), 3.39-3.42, (m,
4H, THF), 6.97-7.05 (m, 12H, Ph), 8.15-8.20 (m, 8H, Ph).
=

Article
Organometallics, Vol. 29, No. 7, 2010 1627
Table 3. Crystallographic Data for Compounds 3-5
3
4
5
formula
fw
color
C
508.90
colorless
monoclinic
P21/c
11.5467(16)
19.957(3)
12.4806(17)
90
105.873(2)
90
2766.4(6)
4
1.222
0.447
1048
25H20AlClP2S2
C50H40Cl2Ga2P4S4
1103.28
colorless
monoclinic
P21/c
11.557(8)
19.892(14)
12.418(8)
90
106.293(11)
90
2740(3)
C25H20ClInP2S2
596.74
colorless
monoclinic
P21/c
11.6775(17)
20.458(3)
12.5404(19)
90
108.184(2)
90
2846.3(7)
4
1.393
1.193
1192
cryst syst
space group
ꢀ
˚
a (A)
ꢀ
˚
b (A)
ꢀ
˚
c (A)
R (deg)
β (deg)
γ (deg)
3
ꢀ
˚
V (A )
Z
2
1.337
1.381
1120
dcalcd (g cm-3
)
μ (mm-1
F(000)
)
cryst size (mm)
2θ range (deg)
index ranges
0.40 ꢀ 0.30 ꢀ 0.20
1.83 to 25.00
-10 e h e 13
-19 e k e 23
-14 e l e 14
14 857
0.40 ꢀ 0.30 ꢀ 0.20
1.84 to 25.00
-13 e h e 13
-23 e k e 23
-14 e l e 8
14 297
0.40 ꢀ 0.30 ꢀ 0.20
1.84 to 25.00
-13 e h e 13
-20 e k e 24
-14 e l e 14
15 234
no. of rflns collected
no. of indep rflns
4867
4819
5013
R1, wR2 (I > 2(σ)I)
R1, wR2 (all data)
goodness of fit, F2
0.0388, 0.0973
0.0537, 0.1036
0.993
0.0524, 0.1126
0.0875, 0.1235
0.901
0.0323, 0.0785
0.0425, 0.0826
0.978
no. of data/restraints/params
)
4867/0/280
0.458 to -0.233
4819/0/280
0.834 to -0.523
5013/0/280
0.805 to -0.386
-3
ꢀ
˚
largest diff peaks (e A
16H, Ph). 13C{1H} NMR (75.5 MHz, THF-d8): δ 26.39
(THF), 68.23 (THF), 127.36, 127.44, 127.52, 128.22, 128.63,
130.25, 131.84, 132.20, 139.53, 140.77 (Ph). 31P{1H} NMR
(121.5 MHz, THF-d8): δ 14.05, 34.98.
˚
Table 4. Selected Bond Distances (A) and Angles (deg) for
Compounds 3-5
[MCl{C(PPh2dS)2}]2
[AlCl{C(PPh2dS)2}]2 (3). A solution of 1 (0.63 g, 1.05 mmol)
in Et2O (20 mL) was added slowly to the solution of AlCl3
(0.07 g, 0.52 mmol) in Et2O (20 mL) at 0 °C with stirring. The
resultant white suspension was raised to ambient temperature
and stirred for 48 h. Volatiles were removed under reduced
pressure. The residue was extracted with CH2Cl2 and filtered.
Addition of THF to the filtrate and concentration gave 3
as colorless crystals. Yield: 0.25 g (93%). Mp: 244.2 °C (dec).
M = Al (3)
M = Ga (4)
M = In (5)
M(1)-C(1A)
M(1)-Cl(1)
M(1)-S(1)
M(1)-S(2)
P(1)-C(1)
P(1)-S(1)
P(2)-C(1)
P(2)-S(2)
1.975(2)
2.169(1)
2.281(1)
2.291(1)
1.722(2)
2.062(1)
1.724(2)
2.062(1)
1.972(4)
2.219(2)
2.294(2)
2.302(2)
1.710(5)
2.054(2)
1.720(5)
2.051(2)
2.173(3)
2.410(1)
2.477(1)
2.485(1)
1.723(3)
2.059(1)
1.718(3)
2.057(1)
Anal. Found: C, 57.95; H, 3.79. Calcd for C25H20AlClP2S2
3
1/6CH2Cl2: C, 57.78; H, 3.92. 1H NMR (300 MHz, THF-d8): δ
7.29-7.39 (m, 12H, Ph), 7.90-7.97 (m, 8H, Ph). 13C{1H} NMR
(75.5 MHz, THF-d8): δ 128.66 (t, m-Ph, 3JP-C = 6.3 Hz), 131.71
(s, p-Ph), 132.58 (t, o-Ph, 2JP-C = 5.3 Hz), 134.34 (d, ipso-Ph,
1JP-C = 85.3 Hz). 31P{1H} (121.5 MHz, THF-d8): δ 32.24.
[GaCl{C(PPh2dS)2}]2 (4). A solution of 1 (0.63 g, 1.05 mmol)
in Et2O (20 mL) was added slowly to the solution of GaCl3
(0.10 g, 0.57 mmol) in Et2O (20 mL) at 0 °C with stirring. The
resultant white suspension was raised to ambient temperature
and stirred for 48 h. Volatiles were removed under reduced
pressure. The residue was extracted with CH2Cl2 and filtered.
After adding THF to the filtrate, it was concentrated and
allowed to stand for a week to give the title compound as
colorless crystals. Yield: 0.06 g (21%). Mp: 279.7 °C (dec). Anal.
C(1A)-M(1)-Cl(1)
C(1A)-M(1)-S(1)
Cl(1)-M(1)-S(1)
C(1A)-M(1)-S(2)
Cl(1)-M(1)-S(2)
S(1)-M(1)-S(2)
C(1)-P(1)-S(1)
C(1)-P(2)-S(2)
P(1)-S(1)-M(1)
P(2)-S(2)-M(1)
P(1)-C(1)-P(2)
P(1)-C(1)-M(1A)
P(2)-C(1)-M(1A)
112.58(8)
116.03(7)
100.81(4)
116.95(8)
100.29(4)
107.91(4)
115.69(8)
114.99(9)
101.27(4)
101.71(3)
116.8(1)
112.0(1)
117.4(1)
99.94(7)
117.9(1)
99.60(6)
107.12(6)
116.3(2)
115.4(2)
101.05(8)
101.73(7)
117.8(3)
116.9(2)
115.7(2)
112.2(1)
119.1(1)
99.68(3)
119.19(8)
99.61(3)
103.70(3)
116.9(1)
116.5(1)
99.14(4)
99.41(4)
121.1(2)
115.4(2)
115.8(2)
118.0(1)
117.1(1)
13C{1H} NMR (75.5 MHz, C6D6): δ 15.68 (Et2O), 20.05 (t, PCP,
JP-C = 101.0 Hz), 25.65 (THF), 66.15 (Et2O), 68.55 (THF),
128.17 (m-Ph), 129.88 (p-Ph), 132.18 (t, o-Ph, 2JP-C= 5.4 Hz),
Found: C, 53.95; H, 3.95. Calcd for C50H40Ga2Cl2P4S4
3
1/4CH2Cl2: C, 53.67; H, 3.63. 1H NMR (400 MHz, THF-d8): δ
7.29-7.40 (m, 12H, Ph), 7.90-7.95 (m, 8H, Ph). 13C{1H} NMR
(100.6 MHz, THF-d8): δ 128.66 (t, m-Ph, 3JP-C = 6.3 Hz), 131.71
140.49 (d, ipso-Ph, JP-C = 93.3 Hz). 31P{1H} NMR (121.5
1
MHz, C6D6): δ 37.61.
2
[MgC(PPh2dS)2(THF)]2 (2). Bun Mg (1.33 mL, 1.33 mmol,
(s, p-Ph), 132.58 (t, o-Ph, JP-C = 5.4 Hz), 134.48 (d, ipso-Ph,
2
1JP-C = 85.6 Hz). 31P{1H} (162.0 MHz, THF-d8): δ 31.86.
[InCl{C(PPh2dS)2}]2 (5). A solution of 1 (0.66 g, 1.10 mmol)
in Et2O (20 mL) was added slowly to the solution of InCl3
(0.11 g, 0.53 mmol) in Et2O (20 mL) at 0 °C with stirring. The
resultant white suspension was raised to ambient temperature
and stirred for 48 h. Volatiles were removed under reduced
pressure. The residue was extracted with CH2Cl2 and filtered.
Addition of THF to the filtrate and concentration gave 5 as
1.0 M solution in heptane) was added slowly to a solution of
CH2(PPh2dS)2 (0.60 g, 1.33 mmol) in THF (70 mL). The
reaction mixture was stirred at 60 °C for 15 h. The precipitate
was filtered. The yellow filtrate was concentrated under reduced
pressure to yield yellow crystals of 2. Yield: 0.54 g (66%). Mp:
208 °C (dec). Anal. Found: C, 63.87; H, 6.08. Calcd for
C58H56Mg2O2P4S4 THF: C, 64.31; H, 5.58. 1H NMR (300
3
MHz, THF-d8): δ 6.98-7.27 (m, 24H, Ph), 7.72-7.82 (m,

1628 Organometallics, Vol. 29, No. 7, 2010
Leung et al.
colorless crystals. Yield: 0.20 g (64%). Mp: 227.5 °C (dec). Anal.
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 of 1-5 are given in the Support-
ing Information.
Found: C, 49.04; H, 3.27. Calcd for C25H20InClP2S2
3
1/4CH2Cl2: C, 49.07; H, 3.34. 1H NMR (400 MHz, THF-d8): δ
7.08-7.41 (m, 12H, Ph), 7.90-7.96 (m, 8H, Ph). 13C{1H} NMR
(100.6 MHz, THF-d8): δ 128.66 (t, m-Ph, 3JP-C = 6.4 Hz), 131.71
(s, p-Ph), 132.58 (t, o-Ph, 2JP-C = 5.4 Hz), 134.47 (d, ipso-Ph, 1JP-C
= 85.9 Hz). 31P{1H} (162.0 MHz, THF-d8): δ 31.87
X-ray Crystallography. Single crystals were sealed in Linde-
mann glass capillaries under nitrogen. X-ray data of 1-5 were
collected on a Bruker SMART CCD diffractrometer with a Mo
KR sealed tube, ω scan mode with an increment of 0.3°. Crystal
data of 1-5 are summarized in Tables 1 and 3. The structures
were solved by direct phase determination using the SHELXL-
97 program package28 and refined by full-matrix least-squares
Acknowledgment. This work was supported by the
Chinese University of Hong Kong Direct Grant
(Project No.2060353).
Supporting Information Available: Details on 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
1-5. This material is available free of charge via the Internet at
http://pubs.acs.org.
(28) Sheldrick, G. M. SHELX-97, Program for Crystal Structure
€
€
Refinement from Diffraction Data; University of Gottingen: Gottingen,
Germany, 1997.