Synthesis, Structural Characterization and Reactivity of a Bis(phosphine)(silyl) Platinum(II) Complex

Article abstract of DOI:10.1002/cjoc.201500418

Treatment of 1,2-C₆H₄(SiH₃)(SiH₃) (1) with Pt(dmpe)(PEt₃)₂ (dmpe=Me₂PCH₂CH₂PMe₂) in the ratio of 1:1 leads to the complex {1,2-C₆H

Full text of DOI:10.1002/cjoc.201500418

NOTE
DOI: 10.1002/cjoc.201500418
Synthesis, Structural Characterization and Reactivity of
a Bis(phosphine)(silyl) Platinum(II) Complex
Yonghua Li,*,a Wenjin Zeng,a Wenyong Lai,a Shigeru Shimada,b Shi Wang,a
Lianhui Wang,a and Wei Huang*,a
a Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM),
Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts &
Telecommunications, Nanjing, Jiangsu 210023, China
b Research Institute for Innovation in Sustainable Chemistry, National Institute of Advanced Industrial Science and
Technology (AIST), Tsukuba Central 5, 1-1-1, Higashi, Tsukuba, Ibaraki 305-8565, Japan
Treatment of 1,2-C6H4(SiH3)(SiH3) (1) with Pt(dmpe)(PEt3)2 (dmpe＝Me2PCH2CH2PMe2) in the ratio of 1∶1
leads to the complex {1,2-C6H4(SiH2)(SiH2)}PtII (dmpe) (2), which can react with proton organic reagent bearing
hydroxy group with low steric hindrance to form a tetra-alkoxy substituted silyl platinum(II) compound (3). Com-
pounds 2 and 3 are the very rare examples of silyl transition-metal complexes derived from this chelating hydrosi-
lane ligand. To the best of our knowledge, there are only 6 examples of silyl metal complexes prepared from this
ligand with such structural features registered in the Cambridge Structural Database, among them, only one silyl
platinum(II) compound is presented. The structures of complexes 2 and 3 were unambiguously determined by mul-
tinuclear NMR spectroscopic studies and single crystal X-ray analysis.
Keywords silyl, chelating, platinum, multinuclear NMR
Introduction
have been studying the stoichiometric reactions of
1,2-disilylbenzenes with group 10 transition-metal com-
plexes and disclosed the formation of a number of
unique complexes with silicon-metal bonds depending
on the metals, the structures of 1,2-disilylbenzenes, and
the ligands.[4]
The chemistry of transition-metal complexes with
metal-silicon bonds has rapidly grown during the last
decades and research continues to prosper in this area
since the first complex containing Si－M bond was
synthesized by Wilkinson and co-workers in 1956.[1]
The most widely employed approach to the formation of
complexes that contain a silicon-transition metal bond
involves the activation of the Si－H bond by low-valent
transition-metal complexes.[2] Hydrosilanes are used as
versatile coreactants in synthetic organosilicon chemis-
try. Since organohydrosilanes (including RSiH3, R2SiH2,
and R3SiH) may contain three, two, or one SiH bonds as
primary, secondary, and tertiary silanes, respectively,
there are many product variations upon their reaction
with transition metal complexes including mononuclear,
dinuclear, or trinuclear frameworks and different valen-
cy.[3]
Silyl platinum complexes have been most exten-
sively studied. This is not only because platinum com-
pounds generally have higher stability than the corre-
sponding palladium and nickel complexes but also be-
cause platinum complexes are the most widely used
catalysts for transformations of organosilicon com-
pounds since the discovery of the Speier’s catalyst.[5]
Herein, we report the reaction of 1,2-disilylbenzene (1)
with Pt(dmpe)(PEt3)2 (dmpe＝Me2PCH2CH2PMe2) to
afford a mononuclear bis(silyl)platinum(II) complex 2
exclusively, and no further reaction of 2 with a second
molecule of 1 takes place (Scheme 1). Moreover, com-
plex 2 has high reactivity towards proton organic re-
agent bearing hydroxy group with low steric hindrance
to form a tetra-alkoxy substituted silyl platinum(II)
compound 3 (Scheme 2). The structures of complexes 2
and 3 were unambiguously determined by multinuclear
NMR spectroscopic studies and single crystal X-ray
analysis.
Our present research focuses on the preparation of
transition-metal complexes containing metal-silicon
bonds with novel structures motifs using sterically
less-demanding chelating silyl ligands, study of the
unique structural properties and thermal stability for the
silyl-metal complexes formed by Si－H activation. We
*
E-mail: iamyhli@njupt.edu.cn; Tel.: 0086-025-85866533; Fax: 0086-025-85866533
Received June 3, 2015; accepted July 17, 2015; published online September 29, 2015.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201500418 or from the author.
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Chin. J. Chem. 2015, 33, 1206—1210

Synthesis, Structural Characterization and Reactivity of a Bis(phosphine)(silyl) Platinum(II) Complex
Experimental
h at room temperature. GC-MS analysis of the mixture
at this stage showed the presence of partially reduced
products. Then, LiAlH4 (0.3 g) was added and the mix-
ture was stirred for another 3 h at room temperature.
After removal of ether under reduced pressure, the re-
maining mixture was extracted with pentane (20 mL×
3), and then filtered through Celite. After evaporation,
the residue was distilled to gave 1,2-disilylbenzene 1
Materials and equipment
1H NMR, 29Si NMR and 31P NMR spectra were re-
corded on Jeol LA500 (for solution NMR). Chemical
shifts are given in ppm using external references (for
solution NMR spectra, tetramethylsilane (0 ppm) for 1H
and 29Si and 85% H3PO4 (0 ppm) for 31P), and coupling
constants are reported in hertz. C, H and N analyses
were taken on a Perkin-Elmer 240C elemental analyzer.
All reagents and solvents were of reagent-grade quality
obtained from commercial suppliers. All solvents were
dried and distilled from Na/benzophenone ketyl. The
solvents were stored over molecular sieves (4 Å). All
manipulations of air-sensitive materials were carried out
under a nitrogen atmosphere using standard Schlenk
tube techniques or in a glove box. 1,2-Bis(dimethyl-
phosphino)ethane (Aldrich) was purchased and used as
received, disilyl hydrosilane 1,2-C6H4 (SiH3)(SiH3) and
Pt(PEt3)4 were prepared according to the relevant litera-
ture method.[4b,6]
1
(0.76 g, 59%). H NMR (CDCl3, 300 MHz) δ: 4.30 (s,
6H), 7.41 (dd, J＝3.5, 5.5 Hz, 2H), 7.68 (dd, J＝3.5, 5.5
Hz, 2H); 13C NMR (CDCl3, 300 MHz) δ: 129.47, 136.52,
137.21; 29Si NMR (CDCl3, 300 MHz) δ: −61.05; IR
(neat) ν: 3053, 2163, 1126, 933, 903, 755, 734, 651
cm−1.
Preparation of {1,2-C6H4(SiH2)(SiH2)}PtII(dmpe)
complex (2)
A mixture of Pt(PEt3)4 (216 mg, 0.32 mmol) and
dmpe (48 mg, 0.32 mmol) in toluene (4 mL) was stirred
at room temperature for 40 min to give Pt(PEt3)2(dmpe).
After removal of volatiles under vacuum, the residual
was dissolved in toluene (4 mL). To this solution was
added hydrosilane (1, 44 mg, 0.32 mmol) at 0 ℃, and
the mixture was stirred at 0 ℃ for 12 h and then at
room temperature for 24 h. Removal of volatiles under
vacuum afforded a light yellow residue, which was
washed with hexane (2 mL×3) and dried under vacuum
to give the product 2 as a colorless solid, 120 mg (78%).
31P{1H} NMR (THF-d8, 202.0 MHz) δ: for 2, 66.35 (s,
Synthesis
Preparation of 1,2-disilylbenzene (1)[4]
To a solution of phenyltris(N,N,N'-trimethyl ethyl-
enediamino)silane (20.4 g, 0.05 mol) in hexane (100 mL)
was added a pentane solution of t-BuLi (1.7 mol/L, 84
mL, 0.114 mol) over 30 min at 0 ℃ under nitrogen.
After stirring at r.t. for 3 h, the solution was added by
using polyethylene tube to a solution of SiC14 (61 g,
0.36 mol) in hexane (50 mL) at −75 ℃ over 1 h. After
addition was completed, the mixture was allowed to
warm to r.t. and stirred for 3 h. The solvents and excess
of SiC14 were removed under reduced pressure at r.t.
After the addition of hexane (50 mL) to the residue,
i-PrOH (90 mL) was added dropwise at 0 ℃. The mix-
ture was stirred at r.t. for 12 h. Volatiles were removed
under vacuum, hexane (140 mL) was added, and the
mixture was filtered through Celite. The filtrate was
further filtered through a short pad of SiO2 to remove a
remaining salt. After evaporation, the residue was sub-
jected to bulb-to-bulb distillation to give 14.5 g (60 %)
of 1,2-bis(triisopropoxysilyl) benzene. The product ob-
tained by bulb-to-bulb distillation was used for the next
1JPt P＝1625 Hz); 1H NMR (THF-d8, 499.1 MHz) δ: for
－
2, 0.51－1.15 (m, 16H, Me2PCH2CH2PMe2), 5.58－
5.67 (m, 4H, SiH2), 7.47 (dd, J＝3, 5 Hz, 2H, aro-
matic-H), 7.69－7.74 (m, 2H, aromatic-H); 29Si{1H}
NMR (THF-d8, 99.1 MHz) δ: for 2, −14.35 (dd, 2JP
＝
－
Si
2
1
149 Hz, JP Si＝13 Hz, JPt Si＝1103 Hz, SiH2). Anal.
－
－
calcd for C12H24P2PtSi2: C 29.93, H 5.02; found C 30.38,
H 5.43.
Preparation of {1,2-C6H4[Si(OCH3)2Si(OCH3)2]}
PtII(dmpe) complex (3)
In a Schlenk tube equipped with a magnetic stirrer
bar, {1,2-C6H4(SiH2) (SiH2)}PtII(dmpe) (241 mg, 0.5
mmol) and dry methanol (6 mL) were placed. The mix-
ture was stirred at room temperature for 3 h under ni-
trogen, and then stirred at 60 ℃ for about 10 h.
Removal of volatiles under vacuum afforded a light
yellow residue, which was washed with hexane (2 mL×
3) and dried under vacuum to give the product 3 as a
colorless solid, 210 mg (70%). 31P{1H} NMR (C6D6,
1
step without further purification. H NMR (CDCl3, 300
MHz) δ: 1.20 (d, J＝6 Hz, 36H), 4.34 (septet, J＝6 Hz,
6H), 7.37 (dd, J＝3.5, 5.5 Hz, 2H), 7.95 (dd, J＝3.5, 5.5
Hz, 2H); 13C NMR (CDCl3, 300 MHz) δ: 25.53, 65.39,
128.30, 136.75, 139.99; 29Si NMR (CDCl3, 300 MHz) δ:
−62.94; IR (neat) ν: 3048, 2974, 1466, 1381, 1371, 1174,
1125, 1038, 886, 750, 704, 538, 505. Anal. calcd for
C24H46O6Si2 (%): C 59.22, H 9.52; found C 59.07, H
9.57.
To an ether suspension (30 mL) of LiAlH4 (0.97 g,
26 mmol) was added dropwise a solution of 1,2-bis(tri-
isopropoxysilyl)benzene (4.6 g, 9.5 mmol) in ether (20
mL) at 0 ℃ over 40 min. The mixture was stirred for 5
1
1
202.0 MHz) δ: for 3, 43.45 (s, JPt P＝1345 Hz); H
－
NMR (C6D6, 499.1 MHz) δ: for 3, 1.58－1.65 (m, 12H,
－Me2P－), 1.71－1.79 (m, 4H, －PCH2CH2P－), 3.34
(s, 12H, Si(OCH3)2), 7.22 (dd, J＝3, 6 Hz, 2H,
aromatic-H), 7.72 (dd, J＝3, 6 Hz, 2H, aromatic-H);
29Si{1H} NMR (C6D6, 99.1 MHz) δ: for 3, 28.43 (dd,
2
2JP Si＝139 Hz, JP Si＝10 Hz, Si(OMe)2). Anal. calcd
－
－
for C16H32O4P2PtSi2: C 31.94, H 5.36; found C 32.43, H
5.72.
Chin. J. Chem. 2015, 33, 1206—1210
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www.cjc.wiley-vch.de
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Li et al.
NOTE
X-ray crystallography
Table 2 Selected bond lengths (Å) and selected bond angles (°)
for 3
The diffraction data were collected at 293 K on a
Bruker Smart APEX CCD diffractometer with Mo Kα
radiation (λ＝0.71073 Å ), and the data reduction was
performed using Bruker SAINT. An absorption correc-
tion was applied using the method of multi-scans. The
structure was solved using direct methods, which yield-
ed the positions of all nonhydrogen atoms. These were
refined first isotropically and then anisotropically. All
the hydrogen atoms were placed in calculated positions
with fixed isotropic thermal parameters and included in
structure factor calculations in the final stage of
full-matrix least-squares refinement. All calculations
were performed using the SHELXTL programs.[7] The
crystallographic data are summarized in Table 1 and
selected geometric parameters are listed in Table 2.
Pt1－Si1
Pt1－P1
Si1－O1
Si2－O3
2.328(3)
2.327(3)
1.669(7)
1.672(9)
Pt1－Si2
2.343(3)
2.323(3)
1.667(11)
1.666(7)
85.13(9)
96.86(9)
94.12(9)
116.8(4)
96.9(4)
Pt1－P2
Si1－O2
Si2－O4
Si1－Pt1－Si2 84.01(9)
P1－Pt1－Si2 176.49(10)
P2－Pt1－Si1 177.61(10)
Pt1－P1－C11 116.7(4)
O1－Si1－O2 102.1(5)
O1－Si1－Pt1 117.6(3)
P1－Pt1－P2
P2－Pt1－Si2
Si1－Pt1－P1
Pt1－P2－C15
O3－Si2－O4
O3－Si2－Pt1
117.8(4)
reactivity toward transition metals can react with
Pt(dmpe)(PEt3)2 (dmpe ＝ Me2PCH2CH2PMe2) in dry
toluene at room temperature in the ratio of 1∶1 to af-
ford the bis(silyl)platinum(II) complex 2 bearing a che-
lating dmpe ligand exclusively (Scheme 1). The whole
reaction process underwent the successive oxidative
addition of the Si－H bond to the Pt(0) center and dis-
sociation of PEt3 molecules. Most of the similar mono-
nuclear bis(silyl) platinum(II) complexes bearing or-
ganophosphorus ligands with low steric hindrance re-
ported previously are thermally unstable and can be par-
tially converted to the corresponding dinuclear platinum
complexes with the bridging silylene. For this silyl co-
ordination compound 2, it was also unstable and NMR
spectra in THF-d8 showed that complex 2 seemed to be
in equilibrium with a certain mixed valent polynuclear
platinum complex in solution. Although monomer 2
could not be obtained as a crystal, 2 can be trapped by
proton organic reagent. Complex 2 has high reactivity
towards proton organic reagent bearing hydroxy group
with low steric hindrance. Treatment of complex 2 with
methanol gives a novel tetra-methoxy substituted silyl
platinum(II) compound 3 (Scheme 2). In addition, no
further reaction of 2 with a second molecule of 1 takes
place even at elevated temperature, which can be mainly
attributed to the high coordination ability of the aliphatic
alkylphosphine ligand dmpe with chelating structure to
the platinum center and the steric effect caused by me-
thyl groups on phosphorus atoms.
Table 1 Crystallographic data for 3
Compound
3
Formula
C16H32O4P2PtSi2
601.63
colorless
Formula weight
Crystal color
Crystal system
monoclinic
Space group
a/Å
Cc
9.2860(19)
17.296(4)
14.360(3)
90
b/Å
c/Å
α/(o)
β/(o)
γ/(o)
102.06(3)
90
Volume/Å3
2255.5(8)
Z
4
T/K
293(2)
1.772
1184
Dx/(Mg•m−3)
F(000)
μ/mm−1
6.486
θ range for data collection/(°)
2.36－27.51
−12≤h≤12, −22≤k≤22,
−18≤l≤18
Index ranges
Measured reflections
11105
5067
Independent reflections
Compounds 2 and 3 are the very rare examples of
silyl transition-metal complexes derived from this che-
lating hydrosilane ligand. To the best of our knowledge,
there are only 6 examples of silyl metal complexes pre-
pared from this ligand with such structural features reg-
istered in the Cambridge Structural Database, among
them, only one silyl platinum(II) compound is pre-
sented.[8]
Data/restraints/parameters
5067/2/234
0.101
Rint
Reflections with I＞2σ(I)
R1 [I＞2σ(I)]
wR2 (all data)
4749
0.052
0.128
Crystals of 3 suitable for single-crystal X-ray analy-
sis were grown by cooling a dimethoxyethane solution
to 0 ℃, and the molecular structure determined at 293
K was unambiguously confirmed by single-crystal
X-ray structure analysis (Figure 1). Tetra-methoxy sub-
stituted silyl complex 3 crystallizes in the monoclinic
Results and Discussion
We have studied the reaction of a chelating hydrosi-
lane, 1,2-bis(silyl)benzene, which has two trihydrosilyl
groups, with group 10 transition-metal complexes. Si-
lane 1, 1,2-disilylbenzene which has relatively high
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Chin. J. Chem. 2015, 33, 1206—1210

Synthesis, Structural Characterization and Reactivity of a Bis(phosphine)(silyl) Platinum(II) Complex
space group Cc (Table 1). The central Pt atom in com-
pound 3 adopts a distorted square-planar P2Si2Pt(II) co-
ordination geometry and is surrounded by two chelating
P atoms, two chelating Si atoms from one hydrosilane
ligand. The bond angles of P2－Pt1－Si1 (177.61(10)°)
and Si1－Pt1－Si2 (84.01(9)o) are slightly greater than
those of the reported similar complex. The average bond
lengths of Pt－Si (2.336(3) Å) and Pt－P (2.325(3) Å)
are slightly shorter than those of the analogous silyl
platinum(II) compound.[8a] There exists some deviation
from the P2PtSi2 plane at the Pt atom which can be at-
tributed to the steric repulsion between the substituent
groups on the silyl and phosphorus ligands (Table 2).
The structures of complexes 2 and 3 were also well
identified by multinuclear NMR spectroscopic studies.
In the 31P{1H} NMR spectrum, the two chemically
Figure 1 The structure of 3, showing the coordination environ-
ment of Pt atom and the hydrogen atoms bound to carbon atoms
are omitted for clarity.
2 bearing a chelating dmpe ligand by successive oxida-
tive addition and reductive elimination reaction of a
kind of poly(silyl) chelating hydrosilane has been estab-
lished. We report the synthesis, preliminary coordination
chemistry studies, thermodynamic behavior and reactiv-
ity toward proton organic reagent bearing hydroxy
group of this new complex. Further applications of these
silyl transition-metal complexes to organic synthesis are
currently in progress.
equivalent phosphorus atoms give rise to a singlet with
1
relatively moderate JPt values which are within the
－
P
typical range of those observed in cis-bis(silyl)bis-
(phosphine)platinum(II) complexes.[9] The signals for
2
P－P coupling with very small JP values in the spec-
－
P
trum suggest that both P atoms are in cis-position. Sig-
nals for SiH2 groups in the proton-decoupled 29Si NMR
spectrum are also consistent with the structure. The SiH2
signals (a doublet of doublets) with a large (149 Hz) and
a small (13 Hz) 2JP Si value, indicate that the SiH2 group
Acknowledgement
－
is in cis-position relative to one P atom and trans to the
other P atom.
This work was financially supported by the National
Key Basic Research Program of China (No.
2014CB648300), the National Natural Science Founda-
tion of China (Nos. 51173082 and 51274159), the Natu-
ral Science Foundation of Jiangsu Province (No.
BK20141425), the Natural Science Foundation of Col-
leges and Universities in Jiangsu Province (No.
13KJB150028), the Priority Academic Program Devel-
opment (PAPD) of Jiangsu Higher Education Institu-
tions and the Ministry of Education of China (No.
IRT1148).
Scheme 1
The reaction of the parent chelating silane,
1,2-C6H4(SiH3)(SiH3) (1) with Pt(dmpe)(PEt3)2 (dmpe ＝
Me2PCH2CH2PMe2) in the ratio of 1∶1, leading to a mononu-
clear complex {1,2-C6H4(SiH2)(SiH2)}-PtII(dmpe) (2)
toluene
Pt(PEt3)4 + Me2PCH2CH2PMe2
Pt(PEt3)2(dmpe) + 2PEt3
r.t.
SiH3
toluene
Pt(PEt3)2(dmpe)
+
0 oC to r.t.
-H2
SiH3
1
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Si
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Chin. J. Chem. 2015, 33, 1206—1210
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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