Reactivity of a tin(II) 1,3-benzodi(thiophosphinoyl)methanediide complex toward gallium, germanium, and zinc compounds

Article abstract of DOI:10.1021/om400141j

The reactivity of the tin(II) 1,3-benzodi(thiophosphinoyl)methanediide complex [{μ-1,3-C₆H₄(PhPS)₂C}Sn]₂ (1) toward GaCl₃, GeCl₄, and ZnEt₂ is described. The reaction of 1 with 1.7 equiv of GeCl₄ in CH ₂Cl₂ at room temperature afforded [1,3-C₆H ₄(PhPS)₂C(GeCl₃)SnCl]₂ (2). Treatment of 1 with 1.7 equiv of ZnEt₂ in refluxing toluene afforded [{1,3-C₆H₄(PhPS)₂CSnEt₂}(μ-ZnS)] ₂ (3). Compound 1 also reacted with 1.7 equiv of GaCl₃ in CH₂Cl₂ to afford [1,3-C₆H₄(PhPS) ₂C(Sn)(GaCl₃)] (4). Compounds 2-4 have been characterized by NMR spectroscopy and X-ray crystallography.

Full text of DOI:10.1021/om400141j

Article
pubs.acs.org/Organometallics
Reactivity of a Tin(II) 1,3-Benzodi(thiophosphinoyl)methanediide
Complex toward Gallium, Germanium, and Zinc Compounds
Yi-Fan Yang, Rakesh Ganguly, Yongxin Li, and Cheuk-Wai So*
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University,
637371 Singapore
S
* Supporting Information
ABSTRACT: The reactivity of the tin(II) 1,3-benzodi(thiophosphinoyl)methanediide complex [{μ-1,3-C6H4(PhPS)2C}Sn]2
(1) toward GaCl3, GeCl4, and ZnEt2 is described. The reaction of 1 with 1.7 equiv of GeCl4 in CH2Cl2 at room temperature
afforded [1,3-C6H4(PhPS)2C(GeCl3)SnCl]2 (2). Treatment of 1 with 1.7 equiv of ZnEt2 in refluxing toluene afforded [{1,3-
C6H4(PhPS)2CSnEt2}(μ-ZnS)]2 (3). Compound 1 also reacted with 1.7 equiv of GaCl3 in CH2Cl2 to afford [1,3-
C6H4(PhPS)2C(Sn)(GaCl3)] (4). Compounds 2−4 have been characterized by NMR spectroscopy and X-ray crystallography.
Chart 1. Low-Valent Metallavinylidene Derivatives (A and
D) and 1,3-Dimetallacyclobutane Derivatives (B and C)
INTRODUCTION
■
The utilization of geminal dianions stabilized by phosphorus-
(V) substituents for the formation of a MC double bond has
attracted much attention in the past few decades.1 Two of the
well-studied examples are [(PPh2S)C2−] and [(PPh2NSiMe3)-
C2−].2 These geminal dianions can coordinate with a variety of
main-group elements,3 transition metals,4 and lanthanides5 to
form bis-phosphorus-stabilized carbene complexes of compo-
sition [(PPh2E)2CM] and [(PPh2E)2CMC(PPh2E)2].
In these complexes, the four electrons of the formal MC
double bond are solely provided by the ligand, which are in
contrast to the Fischer- and Schrock-type carbenes.
Recently, low-valent group 14 metal derivatives [:MC-
(PPh2E)2]2 (M = Ge, Sn, Pb, E = NSiMe3, S) were
synthesized.6 They have either a metallavinylidene structure
(A, Chart 1) or a 1,3-dimetallacyclobutane structure (B and C).
Moreover, the tin(II) derivative [(PPh2NSiMe3)(PPh2S)CSn:]2
(D),7 which comprises both iminophosphinoyl and thiophos-
phinoyl substituents, was synthesized. It has a metallavinylidene
skeleton similar to that of the bisgermavinylidene
[(Me3SiNPPh2)2CGe:]2 (A).6a The reactivities of low-valent
group 14 metallavinylidene derivatives A8 and D9 have been
well studied. They can act as a Lewis base or undergo an 1,2-
addition or cycloaddition toward various transition-metal
complexes and organic and inorganic substrates.8,9 In contrast,
the reactivity of low-valent group 14 1,3-dimetallacyclobutanes
has been less studied. Only a handful of examples have been
reported. For example, Leung et al. showed that the reaction of
[Pb{μ-C(PPh2S)2}]2 (CII) with sulfur formed [PbS{C-
(PPh2S)2}], in which the sulfur atom is inserted into the
Cmethanediide−Pb bonds.6b
In 2012, our group reported the synthesis of the tin(II) 1,3-
benzodi(thiophosphinoyl)methanediide complex [{μ-1,3-
C6H4(PhPS)2C}Sn]2 (1), which contains a 1,3-dimetallacyclo-
butane skeleton.10 Since the tin atoms in 1 contain a lone pair
Received: February 19, 2013
Published: April 22, 2013
© 2013 American Chemical Society
2643
dx.doi.org/10.1021/om400141j | Organometallics 2013, 32, 2643−2648

Organometallics
Article
Scheme 1. Synthesis of 2
Figure 1. Molecular structure of 2 with thermal ellipsoids at the 50% probability level. The solvent molecule and hydrogen atoms are omitted for
clarity. Selected bond lengths (Å) and angles (deg): Sn(1)−S(1) = 2.6289(17), Sn(1)−S(2A) = 2.7274(19), Sn(1)−Cl(4) = 2.5192(19), C(1)−
P(1) = 1.727(8), C(1)−P(2) = 1.731(8), C(1)−Ge(1) = 1.866(8), P(1)−S(1) = 2.036(3), P(2)−S(2) = 2.011(2); S(1)−Sn(1)−S(2A) = 87.12(6),
S(1)−Sn(1)−Cl(4) = 83.55(6), S(2A)−Sn(1)−Cl(4) = 86.38(6), P(1)−C(1)−P(2) = 111.8(4), P(1)−C(1)−Ge(1) = 123.5(4), P(2)−C(1)−
Ge(1) = 124.7(4).
of electrons, we explored its reactivity toward Lewis acidic
aluminum trichloride. The result is astonishing, in that the low-
valent Sn atoms do not form any adduct with AlCl3. Instead,
AlCl3 inserts into the Sn−C bonds and coordinates with the
Cmethanediide atoms to form [1,3-C6H4(PhPS)2C(Sn)(AlCl3)].
This illustrates that the Cmethanediide−Sn bonds in 1 are polar and
the Cmethanediide atom is nucleophilic. Hence, the lone pair of
electrons on the tin atoms is less favorable for bond formation.
In this study, we continue our effort to investigate the reactivity
of 1 with other Lewis acids. Herein, the reactivity of 1 with
germanium tetrachloride, diethylzinc, and gallium trichloride is
reported.
RESULTS AND DISCUSSION
■
Reactivity of 1 toward GeCl4. The reaction of 1 with 1.7
equiv of GeCl4 in CH2Cl2 at room temperature afforded [1,3-
C6H4(PhPS)2C(GeCl3)SnCl]2 (2; Scheme 1) in 69% yield. It is
proposed that the Ge−Cl bond of GeCl4 inserts into the C−Sn
bonds in 1 to form intermediate E. Subsequently, the C−Sn
bond in the intermediate is cleaved and the Sn atom
coordinates with the thiophosphinoyl substituent of another
molecule of E to form 2. The results also illustrate the
nucleophilic character of the Cmethanediide atom in 1. The similar
compound [(PPh2NSiMe3)(PPh2S)C{Rh(cod)}(SnCl)], in
which the Cmethanediide atom bonds to two different metals,
was prepared by a 1,2-addition of [RhCl(cod)]2 with the
2644
dx.doi.org/10.1021/om400141j | Organometallics 2013, 32, 2643−2648

Organometallics
Article
Scheme 2. Synthesis of 3
Figure 2. Molecular structure of 3 with thermal ellipsoids at the 50% probability level. Disordered ethyl and hydrogen atoms are omitted for clarity.
Selected bond lengths (Å) and angles (deg): Zn(1)−S(2) = 2.3445(5), Zn(1)−S(3) = 2.3394(5), Zn(1)−S(1) = 2.3785(5), Zn(1)−S(1A) =
2.3741(5), Sn(1)−C(1A) = 2.1070(17), Sn(1)−C(2) = 2.162(7), Sn(1)−C(4) = 2.165(2), Sn(1)−S(1) = 2.4277(4), P(1)−C(1) = 1.7091(18),
P(2A)−C(1) = 1.7117(18), P(1)−S(2) = 2.0324(6), P(2A)−S(3A) = 2.0279(6); Zn(1)−S(1)−Zn(1A) = 75.185(15), S(1)−Zn(1)−S(1A) =
104.816(15), S(2)−Zn(1)−S(3) = 109.848(18), P(2)−C(1A)−P(1A) = 111.62(10), P(2)−C(1A)−Sn(1) = 123.45(9), P(1A)−C(1A)−Sn(1) =
119.29(9), C(1A)−Sn(1)−S(1) = 103.20(5).
stannavinylidene derivative [(PPh2NSiMe3)(PPh2S)CSn:]2
(D).9b
Compound 2 was isolated as a highly air- and moisture-
Å).11 The Sn(1)−S(2A) bond (2.7274(19) Å) is longer than
the Sn(1)−S(1) bond but is comparable to that in 1
(2.7174(6) Å).10 The C−P bonds (1.727(8) and 1.731(8) Å)
are shortened and P−S bonds (2.036(3) and 2.011(2) Å) are
lengthened in comparison with those in [1,3-
C6H4(PhPS)2CH2] (C−P = 1.8229(14), 1.8373(14) Å; P−S
= 1.9463(5), 1.9498(5) Å).10 The results indicate that there is a
considerable electron delocalization throughout the backbone
of the ligand. The C(1)−Ge(1) bond (1.866(8) Å) is
comparable to the reported C−Ge single bonds (1.90−2.05
Å).12
Reactivity of 1 toward ZnEt2. The reaction of 1 with 1.7
equiv of ZnEt2 in refluxing toluene afforded a mixture of [{1,3-
C6H4(PhPS)2CSnEt2}(μ-ZnS)]2 (3; Scheme 2), SnEt4, [1,3-
C6H4(PhPS)(PhP)CH2], and unidentified products, which was
confirmed by NMR spectroscopy and mass spectrometry. The
reaction mixture was filtered, and compound 3 was isolated as a
highly air- and moisture-sensitive colorless crystalline solid in
16% yield after concentration of the filtrate. Although the
mechanism of the reaction is unknown as yet, on the basis of
the experimental results, we propose that the reaction proceeds
sensitive colorless crystalline solid, which is soluble only in
1
CH2Cl2. The H and 13C NMR spectra display resonances for
the phenyl protons. The 13C NMR spectrum shows a triplet at
δ 54.10 ppm (JP−C = 15.3 Hz) for the Cmethanediide atom in 2.
The 31P NMR spectrum displays one singlet at δ 46.44 ppm for
the PCP nuclei. The 119Sn NMR resonance (δ 75.30 ppm,
triplet, 2JSn−P = 11.9 Hz) lies between those of [(PPh2NSiMe3)-
(PPh2S)C{Rh(cod)}(SnCl)] (δ 110.7 ppm)9b and [HC-
(PPh2S)2SnCl] (δ −129.6 ppm).1b
The molecular structure of 2 is shown in Figure 1. The
C(8)C(13)P(2)C(1)P(1) least-squares plane is nearly orthog-
onal to the P(1)S(1)S(2)P(2) least-squares plane (dihedral
angle 82.0°). The tin atoms are bridged by two thiophosphinoyl
substituents and adopt a distorted-trigonal pyramidal-geometry
(sum of bond angles 257.1°). These geometries indicate that
the tin atoms possess a high-s-character lone pair. The Sn(1)−
S(1) bond (2.6289(17) Å) is comparable to that of the aryl
tin(II) dithiocarboxylate [:Sn(Ar){S2CAr}] (average 2.659
2645
dx.doi.org/10.1021/om400141j | Organometallics 2013, 32, 2643−2648

Organometallics
Article
Scheme 3. Canonical Forms of 3
Scheme 4. Synthesis of 4
through an oxidative addition of 1 with ZnEt2 to form the
stannaethene intermediate “1,3-C6H4(PhPS)2CSnEt2” (Scheme
S1; see the Supporting Information). Subsequently, ZnEt2
reacts with 2 equiv of the intermediate “1,3-
C6H4(PhPS)2CSnEt2” to form 3, SnEt4, and transient “1,3-
C6H4(PhPS)(PhP)C:”. The latter abstracts two protons from
the solvent to form [1,3-C6H4(PhPS)(PhP)CH2]. The results
are similar to the oxidation of the base-stabilized stannaviny-
lidene derivative [(PPh2NSiMe3)(PPh2S)CSn:]2 (D) with
elemental sulfur to afford the unstable 2-stannathiomethane-
diide intermediate “(PPh2NSiMe3)(PPh2S)CSnS”, which then
decomposes to form [(PPh2NSiMe3)(PPh2S)CH2] and [{(μ-
S)SnC(PPh2NSiMe3)(PPh2S)}3Sn(μ3-S)].9a In addition, Chiv-
ers et al. reported that the intermediate [:C(PPh2S)2] dimerizes
to form [(SPh2P)2C2(PPh2)2S2], which contains a six-
membered C2P2S2 ring.13 However, such a dimerization of
“1,3-C6H4(PhPS)(PhP)C:” cannot be observed in the reaction;
instead, [1,3-C6H4(PhPS)(PhP)CH2] is formed.
of bridging Zn−S bond lengths (2.281−2.425 Å).15 The
C(1A)−Sn(1) bond length (2.1070(17) Å) lies between those
of 1 (2.334(2) and 2.301(2) Å)10 and the stannaethene
[{(Me3Si)2CH}2SnC{(BtBu)2C(SiMe3)2}] (2.025(4) Å).16
The C(1A)−Sn(1) bond is also shorter than the C(2/4)−
Sn(1) bonds (2.162(7) and 2.165(2) Å). The results indicate
that the C(1A)−Sn(1) bond is intermediate between a single
and a double bond. Moreover, on comparison of the bond
lengths of the C(PS)2 skeleton (P−C = 1.7091(18),
1.7117(18) Å; P−S = 2.0324(6), 2.0279(6) Å) with those of
[1,3-C6H4(PhPS)2CH2]10 and [{HC(PPh2S)2}2Zn] (P−C =
1.715(2), 1.722(2) Å; P−S = 2.0340(8), 2.0428(8) Å),14 there
is an electron delocalization along the C(PS)2 skeleton. Thus, it
is suggested that compound 3 should be a resonance hybrid of
the canonical formulas I and II (Scheme 3).
Reactivity of 1 toward GaCl3. The reaction of 1 with 1.7
equiv of GaCl3 in CH2Cl2 afforded [1,3-C6H4(PhPS)2C(Sn)-
(GaCl3)] (4; Scheme 4) in 71% yield, which was confirmed by
NMR spectroscopy. Compound 4 was cocrystallized with its
dimer 4d (Chart 2) in a ratio of 2:1 in CH2Cl2, which was
1
Compound 3 is sparingly soluble in CH2Cl2. The H NMR
spectrum displays resonances for the ethyl and phenyl protons.
The 13C NMR signal for the PCP atom cannot be observed.
The 31P spectrum shows a singlet with satellites due to coupling
to the Sn nuclei at δ 51.65 ppm (2JSn−P = 43.3 Hz). The 119Sn
Chart 2. Dimeric Form of 4
2
NMR resonance (δ 53.11 ppm, triplet, JSn−P = 41.1 Hz) lies
between those of the base-stabilized stannavinylidene derivative
[(PPh2NSiMe3)(PPh2S)CSn:]2 (D, δ 132.1 ppm)9b and 1 (δ
26.3 ppm).10
The molecular structure of 3 is shown in Figure 2. With a
C6H4P2C ring as a base, compound 3 has a triple-decker
structure linked by the Sn and S atoms. The Zn atoms are
bridged between the thiophosphinoyl substituents and
coordinated with the S(1/1A) atoms, which adopt a tetrahedral
geometry. The P(1)S(2)Zn(1)S(3)P(2)P(1A)S(2A)Zn(1A)S-
(3A) least-squares plane is nearly orthogonal to the Zn(1)-
S(1)Zn(1A)S(1A) least-squares plane (dihedral angle 82.6°).
The Zn(1)−S(2) (2.3445(5) Å) and Zn(1)−S(3) bonds
(2.3394(5) Å) are comparable to those in [{HC(PPh2S)2}2Zn]
(2.3490(6) and 2.3500(6) Å).14 The Zn(1)−S(1) and Zn(1)−
S(1A) bonds (2.3785(5) and 2.3741(5) Å) are within the range
confirmed by X-ray crystallography (see below). The results
show that the low-valent Sn atoms in 1 do not form any adduct
with GaCl3. Instead, the reaction appears to proceed via an
insertion of GaCl3 into the Sn−C bonds of 1 to form 4. The
lighter congener [1,3-C6H4(PhPS)2C(Sn)(AlCl3)] was synthe-
sized by the reaction of 1 with 2 equiv of AlCl3.10
2646
dx.doi.org/10.1021/om400141j | Organometallics 2013, 32, 2643−2648

Organometallics
Article
Compounds 4 and 4d were isolated as a highly air- and
moisture-sensitive colorless cocrystalline solid. In compound 4
(Figure 3), the Sn(1) atom is coordinated with the
spectroscopy. The 31P NMR of cocrystals in CDCl3 shows a
singlet with satellites due to coupling to the Sn nuclei at δ 58.27
ppm (2JSn−P = 164.7 Hz). The 31P NMR at −95 °C still shows a
singlet with satellites at δ 57.53 ppm (2JSn−P = 147.4 Hz). The
results indicate that compound 4d dissociates in solution to
form compound 4. Moreover, the 119Sn NMR spectrum
displays a triplet at δ −157.83 ppm (2JSn−P = 176.5 Hz),
which is comparable to that of [1,3-C6H4(PhPS)2C(Sn)-
(AlCl3)] (−140.25 ppm).10
In conclusion, compound 1 shows different reactivity toward
Lewis acids. The Ge−Cl bond of GeCl4 undergoes an insertion
with 1 to form [1,3-C6H4(PhPS)2C(GeCl3)SnCl]2 (2). In
contrast, GaCl3 undergoes an insertion with 1 to form [1,3-
C6H4(PhPS)2C(Sn)(GaCl3)] (4), in which the Cmethanediide
atom coordinates to GaCl3. The reaction of 1 with ZnEt2
appears to proceed through the oxidative addition of the Sn
atom in 1, followed by further rearrangement with ZnEt2 to
form [{1,3-C6H4(PhPS)2CSnEt2}(μ-ZnS)]2 (3).
EXPERIMENTAL SECTION
■
All manipulations were carried out under an inert atmosphere of
dinitrogen gas by standard Schlenk techniques. CH2Cl2 was dried over
and distilled over CaH2 prior to use. Toluene was dried and distilled
over Na/K alloy prior to use. 1 was prepared as described in the
literature.10 The H, 13C, 31P, 31P CPMAS, and 119Sn NMR spectra
1
were recorded on a JEOL ECA 400 spectrometer. The chemical shifts
δ are relative to external references SiMe4 for 1H and 13C, 85% H3PO4
for 31P, Me4Sn for 119Sn, and ammonium dihydrogen phosphate for
31P CPMAS. Elemental analyses were performed by the Division of
Chemistry and Biological Chemistry, Nanyang Technological
University. Melting points were measured in sealed glass tubes and
were not corrected.
Figure 3. Molecular structures of (top) 4 and (bottom) 4d (50%
thermal ellipsoids) in an asymmetric unit. Solvent molecules and
hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and
angles (deg): 4, C(1)−Sn(1) = 2.419(3), C(1)−Ga(1) = 1.973(3),
Sn(1)−S(1) = 2.6970(8), Sn(1)−S(2) = 2.6662(7), P(1)−C(1) =
1.761(3), P(2)−C(1) = 1.760(3), P(1)−S(1) = 2.0134(10), P(2)−
S(2) = 2.0219(10), Sn(1)−C(1)−Ga(1) = 98.80(11), S(1)−Sn(1)−
S(2) = 107.73(2), S(1)−Sn(1)−C(1) = 74.01(6), S(2)−Sn(1)−C(1)
= 73.60(6); 4d, C(20)−Sn(2) = 2.397(3), C(20)−Ga(2) = 1.996(3),
Sn(2)−S(3) = 2.6434(7), Sn(2)−S(4) = 2.6667(7), P(3)−C(20) =
1.764(3), P(4A)−C(20) = 1.773(3), P(3)−S(3) = 2.0099(10), P(4)−
S(4) = 2.0282(9), Sn(2)−C(20)−Ga(2) = 100.48(11), S(3)−Sn(2)−
S(4) = 86.54(2), S(3)−Sn(2)−C(20) = 74.62(6), S(4)−Sn(2)−
C(20) = 96.37(6).
[1,3-C6H4(PhPS)2C(SnCl)(GeCl3)]2 (2). GeCl4 (1.0 mL, 1.0 mmol,
1.0 M in toluene) was added to a solution of 1 (0.57 g, 0.6 mmol) in
CH2Cl2 (30 mL) at ambient temperature. The resulting white
suspension was stirred overnight. After filtration and concentration of
the filtrate, compound 2 was afforded as colorless crystals. The white
residue is also compound 2, which was confirmed by NMR
spectroscopy. Yield: 0.54 g (69%). Mp: 190 °C dec. Anal. Calcd for
C38H28Cl8Ge2P4S4Sn2: C, 32.53; H, 2.01. Found: C, 32.17; H, 2.09. 1H
NMR (395.9 MHz, THF-d8, 22.7 °C): δ 7.41−7.47 (m, 4H, Ph and
C6H4), 7.51−7.62 (m, 16H, Ph and C6H4), 8.01−8.07 ppm (m, 8H,
Ph and C6H4). 13C{1H} NMR (99.5 MHz, THF-d8, 21.8 °C): δ 54.10
(JP−C = 15.3 Hz, PCP), 128.38−129.52 (m, Ph and C6H4), 132.39−
132.30 (m, Ph and C6H4), 142.13 ppm (t, JP−C = 54.6 Hz, Cipso of Ph
or C6H4). 31P{1H} NMR (160.3 MHz, THF-d8, 24.6 °C): δ 46.44
ppm. 119Sn{1H} NMR (147.6 MHz, THF-d8, 23.6 °C): δ 75.30 ppm
thiophosphinoyl substituents and the Cmethanediide atom. The
Sn(1)S(1)P(1)C(1)P(2)S(2) metallacycle adopts a pseudo-
boat conformation in which the C(1) and Sn(1) atoms are
displaced from the P(1)S(1)S(2)P(2) least-squares plane by
1.033 and 1.512 Å, respectively. The geometry around the
Sn(1) atom is distorted trigonal pyramidal (sum of bond angles
255.34°). This indicates that there is a stereoactive lone pair of
electrons at the Sn(1) atom. Compound 4d is a dimer of
compound 4, in which the tin atoms are bridged between the
thiophosphinoyl substituents of two ligands. The C−Sn bonds
in 4 (2.419(3) Å) and 4d (2.397(3) Å) are slightly longer than
those in 1 (2.334(2) and 2.301(2) Å). The C−Ga bonds in 4
(1.973(3) Å) and 4d (1.996(3) Å) are comparable to that in
[(IMes)GaCl3] (1.954(4) Å; IMes = N,N′-bis(2,4,6-
trimethylphenyl)imidazol-2-ylidene).17
2
(t, JSn−P = 11.9 Hz).
[{1,3-C6H4(PhPS)2CSnEt2}(μ-ZnS)]2 (3). ZnEt2 (1.0 mL, 1.0
mmol, 1.0 M in hexane) was added to a suspension of 1 (0.57 g,
0.6 mmol) in toluene (20 mL). The resulting mixture was refluxed at
140 °C overnight to give an orange solution. After filtration and
concentration of the filtrate, 3 was afforded as colorless crystals. Yield:
0.10 g (16%). Mp: 284 °C dec. Anal. Calcd for C46H48P4S6Sn2Zn2: C,
1
42.98; H, 3.76. Found: C, 42.88; H, 3.73. H NMR (399.5 MHz,
3
CDCl3, 23.4 °C): δ 1.05 (t, 12H, JH−H = 7.8 Hz, CH2CH3), 1.17−
1.32 (m, 8H, CH2CH3), 7.30−7.40 (m, 12H, Ph and C6H4), 7.48−
7.52 (m, 4H, Ph and C6H4), 7.77−7.84 ppm (m, 12H, Ph and C6H4).
13C{1H} NMR (99.5 MHz, CDCl3, 23.8 °C): δ 9.31 (t, 3JP−C = 3.7 Hz,
SnCH2CH3), 10.60 (s, SnCH2CH3), 128.10 (s, Cpara of Ph), 128.20 (d,
JP−C = 5.0 Hz, Ph or C6H4), 128.63−128.97 (m, Ph and C6H4), 130.28
(t, JP−C = 5.0 Hz, Ph or C6H4), 131.03 (d, JC−P = 69.6 Hz, Cipso of Ph
or C6H4). 31P{1H} NMR (160.3 MHz, CDCl3, 24.6 °C): δ 51.65 ppm
(2JSn−P = 43.3 Hz). 119Sn{1H} NMR (147.6 MHz, CDCl3, 24.5 °C): δ
The coexistence of compounds 4 and 4d in the solid state
can be confirmed by 31P CPMAS NMR spectroscopy, in which
two signals at δ 55.97 and 59.82 ppm for 4d and one singlet at
δ 57.25 ppm for 4 are observed. However, in solution, only
compound 4 is observed, which is confirmed by NMR
2
53.11 ppm (t, JSn−P = 41.1 Hz).
[1,3-C6H4(PhPS)2C(Sn)(GaCl3)] (4). A solution of 1 (0.57 g, 0.6
mmol) in CH2Cl2 (30 mL) was added to a solution of GaCl3 (0.18 g,
2647
dx.doi.org/10.1021/om400141j | Organometallics 2013, 32, 2643−2648

Organometallics
Article
1.0 mmol) in CH2Cl2 (10 mL) at ambient temperature. The resulting
yellow suspension was stirred overnight to give a white suspension.
After filtration and concentration of the filtrate, 4 and its dimer 4d
(2:1) were afforded as colorless cocrystals. Yield: 0.53 g (71%). Mp:
256 °C dec. Anal. Calcd for C19H14Cl3GaP2S2Sn: C, 34.41; H, 2.13.
Found: C, 34.24; H, 2.10. 31P CPMAS (161.73 MHz, spinning speed
10 kHz): δ 55.97 (s, 4d), 57.25 (s, 4), 59.82 (s, 4d). In solution, only 4
is observed. 1H NMR (399.5 MHz, CDCl3, 23.0 °C): δ 7.42−7.54 (m,
6H, Ph and C6H4), 7.60−7.69 (m, 4H, Ph and C6H4), 7.78−7.84 ppm
(m, 4H, Ph and C6H4). 13C{1H} NMR (99.5 MHz, CDCl3, 23.4 °C):
δ 128.90−129.42 (m, Ph and C6H4), 132.35−132.57 (m, Ph and
C6H4), 134.14−134.21 (m, Ph and C6H4), 134.40 ppm (s, Cpara of
Ph). 31P{1H} NMR (160.3 MHz, CDCl3, 23.6 °C): δ 58.27 ppm
(2JP−Sn = 164.7 Hz). 119Sn{1H} NMR (147.6 MHz, CDCl3, 23.5 °C): δ
(4) (a) Fustier, M.; Le Goff, X. F.; Le Floch, P.; Mez
Chem. Soc. 2010, 132, 13108. (b) Cavell, R. G.; Kamalesh Babu, R. P.;
Kasani, A.; McDonald, R. J. Am. Chem. Soc. 1999, 121, 5805.
(c) Cantat, T.; Ricard, L.; Mezailles, N.; Le Floch, P. Organometallics
́
2006, 25, 6030. (d) Jones, N. D.; Lin, G.; Gossage, R. A.; McDonald,
R.; Cavell, R. G. Organometallics 2003, 22, 2832. (e) Cantat, T.;
́
ailles, N. J. Am.
Mez
2004, 43, 6382. (f) Cantat, T.; Demange, M.; Mez
Jean, Y.; Le Floch, P. Organometallics 2005, 24, 4838. (g) Fustier-
Boutignon, M.; Heuclin, H.; Le Goff, X. F.; Mezailles, N. Chem.
Commun. 2012, 48, 3306.
(5) (a) Cantat, T.; Jaroschik, F.; Ricard, L.; Le Floch, P.; Nief, F.;
Mezailles, N. Organometallics 2006, 25, 1329. (b) Cantat, T.; Jaroschik,
F.; Nief, F.; Ricard, L.; Mezailles, N.; Le Floch, P. Chem. Commun.
2005, 5178. (c) Cantat, T.; Arliguie, T.; Noel, A.; Thuery, P.;
ailles, N. J. Am. Chem. Soc. 2009,
131, 963. (d) Tourneux, J.-C.; Berthet, J.-C.; Thuery, P.; Mezailles, N.;
Le Floch, P.; Ephritikhine, M. Dalton Trans. 2010, 39, 2494.
(e) Tourneux, J.-C.; Berthet, J.-C.; Cantat, T.; Thuery, P.; Mezailles,
N.; Le Floch, P.; Ephritikhine, M. Organometallics 2011, 30, 2957.
(f) Tourneux, J.-C.; Berthet, J.-C.; Cantat, T.; Thuery, P.; Mezailles,
́
ailles, N.; Ricard, L.; Jean, Y.; Le Floch, P. Angew. Chem., Int. Ed.
́
ailles, N.; Ricard, L.;
́
́
́
2
−157.83 ppm (t, JSn−P = 176.5 Hz).
́
̈
X-ray Data Collection and Structural Refinement. Intensity
data for compounds 2−4 were collected using a Bruker APEX II
diffractometer. The crystals of 2−4 were measured at 103(2) K. The
structures were solved by direct phase determination (SHELXS-97)
and refined for all data by full-matrix least-squares methods on F2.18 All
non-hydrogen atoms were subjected to anisotropic refinement. The
hydrogen atoms were generated geometrically and allowed to ride on
their respective parent atoms; they were assigned appropriate isotopic
thermal parameters and included in the structure factor calculations.
The disordered ethyl substituents in compound 3 were treated with
the appropriate restraints (see the Supporting Information). The X-ray
crystallographic data of 2−4 are summarized in Table S1 (see the
Supporting Information).
Ephritikhine, M.; Le Floch, P.; Mez
́
́
́
́
́
́
́
N.; Ephritikhine, M. J. Am. Chem. Soc. 2011, 133, 6162. (g) Ma, G.;
Ferguson, M. J.; McDonald, R.; Cavell, R. G. Inorg. Chem. 2011, 50,
6500. (h) Mills, D. P.; Moro, F.; McMaster, J.; van Slageren, J.; Lewis,
W.; Blake, A. J.; Liddle, S. T. Nat. Chem. 2011, 3, 454. (i) Cooper, O.
J.; Mills, D. P.; McMaster, J.; Moro, F.; Davies, E. S.; Lewis, W.; Blake,
A. J.; Liddle, S. T. Angew. Chem., Int. Ed. 2011, 50, 2383. (j) Ren, W.;
Deng, X.; Zi, G.; Fang, D.-C. Dalton Trans. 2011, 40, 9662. (k) Mills,
D. P.; Cooper, O. J.; Tuna, F.; McInnes, E. J. L.; Davies, E. S.;
McMaster, J.; Moro, F.; Lewis, W.; Blake, A. J.; Liddle, S. T. J. Am.
Chem. Soc. 2012, 134, 10047.
ASSOCIATED CONTENT
* Supporting Information
■
S
(6) (a) Leung, W.-P.; Wang, Z.-X.; Li, H.-W.; Mak, T. C. W. Angew.
Chem., Int. Ed. 2001, 40, 2501. (b) Leung, W.-P.; Wan, C.-L.; Kan, K.-
W.; Mak, T. C. W. Organometallics 2010, 29, 814.
(7) Guo, J.; Lau, K.-C.; Xi, H.-W.; Lim, K. H.; So, C.-W. Chem.
Commun. 2010, 46, 1929.
(8) (a) Leung, W.-P.; So, C.-W.; Wang, J.-Z.; Mak, T. C. W. Chem.
Commun. 2003, 248. (b) Leung, W.-P.; So, C.-W.; Kan, K.-W.; Chan,
H.-S.; Mak, T. C. W. Inorg. Chem. 2005, 44, 7286. (c) Leung, W.-P.;
So, C.-W.; Kan, K.-W.; Chan, H.-S.; Mak, T. C. W. Organometallics
2005, 24, 5033. (d) Leung, W.-P.; Kan, K.-W.; So, C.-W.; Mak, T. C.
W. Appl. Organomet. Chem. 2007, 21, 814. (e) Leung, W.-P.; So, C.-
W.; Wang, Z.-X.; Wang, J.-Z.; Mak, T. C. W. Organometallics 2003, 22,
4305.
CIF files, tables, and a figure giving X-ray data for 2−4,
crystallographic data of 2−4, a proposed mechanism for the
formation of 3, and the restraints for solving the disorder of the
ethyl groups in 3. This material is available free of charge via the
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail for C.-W.S.: CWSo@ntu.edu.sg.
■
Notes
The authors declare no competing financial interest.
(9) (a) Guo, J.-Y.; Xi, H.-W.; Nowik, I.; Herber, R. H.; Li, Y.; Lim, K.
H.; So, C.-W. Inorg. Chem. 2012, 51, 3996. (b) Guo, J.-Y.; Li, Y.;
Ganguly, R.; So, C.-W. Organometallics 2012, 31, 3888.
(10) Yang, Y.-F.; Foo, C.; Ganguly, R.; Li, Y.; So, C.-W.
Organometallics 2012, 31, 6538.
ACKNOWLEDGMENTS
This work was supported by the Academic Research Fund Tier
1 (RG 57/11).
■
(11) Weidenbruch, M.; Grobecker, U.; Saak, W.; Peters, E.-M.;
Peters, K. Organometallics 1998, 17, 5206.
REFERENCES
■
(1) (a) Liddle, S. T.; Mills, D. P.; Wooles, A. J. Chem. Soc. Rev. 2011,
40, 2164. (b) Liddle, S. T.; Mills, D. P.; Wooles, A. J. Organomet.
Chem. 2010, 36, 29. (c) Izod, K. Coord. Chem. Rev. 2002, 227, 153.
(12) Baines, K. M.; Stibbs, W. G. Coord. Chem. Rev. 1995, 145, 157.
(13) Konu, J.; Chivers, T. Chem. Commun. 2008, 4995.
(14) Thirumoorthi, R.; Chivers, T. Eur. J. Inorg. Chem. 2012, 3061.
(15) Bochmann, M.; Bwembya, G.; Grinter, R.; Lu, J.; Webb, K. J.;
Williamson, D. J.; Hursthouse, M. B.; Mazid, M. Inorg. Chem. 1993, 32,
532.
(16) Gamer, M. T.; Roesky, P. W. Z. Anorg. Allg. Chem. 2001, 627,
877.
́
(17) Marion, N.; Escudero-Adan, E. C.; Benet-Buchholz, J.; Stevens,
E. D.; Fensterbank, L.; Malacria, M.; Nolan, S. P. Organometallics
2007, 26, 3256.
́
(d) Cantat, T.; Mezailles, N.; Auffrant, A.; Le Floch, P. Dalton Trans.
2008, 1957. (e) Jones, N. D.; Cavell, R. G. J. Organomet. Chem. 2005,
690, 5485. (f) Panda, T. K.; Roesky, P. W. Chem. Soc. Rev. 2009, 38,
2782.
(2) (a) Ong, C. M.; Stephan, D. W. J. Am. Chem. Soc. 1999, 121,
2939. (b) Cantat, T.; Ricard, L.; Le Floch, P.; Mezailles, N.
́
Organometallics 2006, 25, 4965. (c) Hull, K. L.; Noll, B. C.;
Henderson, K. W. Organometallics 2006, 25, 4072. (d) Hull, K. L.;
Carmichael, I.; Noll, B. C.; Henderson, K. W. Chem. Eur. J. 2008, 14,
3939. (e) Orzechowski, L.; Jansen, G.; Harder, S. Angew. Chem., Int.
Ed. 2009, 48, 3825. (f) Orzechowski, L.; Jansen, G.; Harder, S. J. Am.
Chem. Soc. 2006, 128, 14676.
(18) Sheldrick, G. M. SHELXL-97; Universitat Gottingen, Gottingen,
̈
̈
̈
Germany, 1997.
(3) (a) Foo, C.; Lau, K.-C.; Yang, Y.-F.; So, C.-W. Chem. Commun.
2009, 6816. (b) Leung, W.-P.; Chan, Y.-C.; Mak, T. C. W. Inorg.
Chem. 2011, 50, 10517. (c) Thirumoorthi, R.; Chivers, T.; Vargas-
Baca, I. Dalton Trans. 2011, 40, 8086.
2648
dx.doi.org/10.1021/om400141j | Organometallics 2013, 32, 2643−2648