Synthesis, structural characterization and reactivity towards phenol of a bis(silyl) platinum(II) complex

Article abstract of DOI:10.1016/j.ica.2016.07.024

The reaction of 1,2-C₆H₄(SiMe₂H)(SiH₃) (1) with Pt(dmpe)(PEt₃)₂(dmpe?=?Me₂PCH₂CH₂PMe₂) in the ratio of 1:1 yields the complex {1,2-C₆H₄(SiMe₂)(SiH₂)}Pt^II(dmpe) (2), which has unique reactivity towards sterically unhindered phenol to form an unusual diphenoxy substituted (bis)silyl platinum(II) compound (3). Only 6 examples of bis(silyl) platinum(II) complexes prepared from this chelating hydrosilane ligand have been registered in the Cambridge Structural Database. The structure of complex (3) was unambiguously determined by single crystal X-ray analysis and multinuclear NMR spectroscopic studies.

Full text of DOI:10.1016/j.ica.2016.07.024

Inorganica Chimica Acta 451 (2016) 157–161
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Research paper
Synthesis, structural characterization and reactivity towards phenol
of a bis(silyl) platinum(II) complex
⇑
⇑
Shuang-Shuang Sun, Jin-Fei Guo, Shi Wang , Chao Huang, Jia-Yi Zhu, Yong-Hua Li , Wei Huang
Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), National Synergetic Innovation Center for Advanced Materials
(SICAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 18 May 2016
Received in revised form 7 July 2016
Accepted 13 July 2016
Available online 16 July 2016
The reaction of 1,2-C6H4(SiMe2H)(SiH3) (1) with Pt(dmpe)(PEt3)2 (dmpe = Me2PCH2CH2PMe2) in the ratio
of 1:1 yields the complex {1,2-C6H4(SiMe2)(SiH2)}PtII(dmpe) (2), which has unique reactivity towards
sterically unhindered phenol to form an unusual diphenoxy substituted (bis)silyl platinum(II) compound
(3). Only 6 examples of bis(silyl) platinum(II) complexes prepared from this chelating hydrosilane ligand
have been registered in the Cambridge Structural Database. The structure of complex (3) was unambigu-
ously determined by single crystal X-ray analysis and multinuclear NMR spectroscopic studies.
Ó 2016 Elsevier B.V. All rights reserved.
Keywords:
Chelating
Silyl
Platinum
Phenol
Multinuclear NMR
1. Introduction
Among silyl-transition-metal complexes, those of platinum
have been most extensively studied. This is not only because
The preparation and reaction of silyl transition-metal com-
plexes have attracted significant interest during the last decades
since the first complex containing Si–M bond was synthesized by
Wilkinson and co-workers in 1956 [1]. The reaction of hydrosilanes
with low-valent transition-metal complexes via Si–H bond activa-
tion is one of the most important methods for preparing silyl tran-
sition-metal complexes [2]. Hydrosilanes are used as versatile
coreactants in synthetic organosilicon chemistry. Since organohy-
drosilanes (including RSiH3, R2SiH2, and R3SiH) may contain one,
two, or three SiH bonds as primary, secondary, and tertiary silanes,
respectively, there are many product variations upon their reaction
with transition metal complexes including mononuclear, dinu-
clear, or trinuclear frameworks and different valency [3].
(silyl)platinum complexes generally have higher stability than
the corresponding palladium and nickel complexes but also
because platinum complexes are the most widely used catalysts
for transformations of organosilicon compounds since the
discovery of the Speier’s catalyst [5]. Herein we report the reaction
of 1-(dimethylsilyl)-2-silylbenzene with Pt(dmpe)(PEt3)2 (dmpe =
Me2PCH2CH2PMe2) to give a mononuclear bis(silyl) platinum(II)
complex 2. This silyl metal compound can react readily with
sterically unhindered phenol to form an unusual di-phenoxy sub-
stituted silyl platinum(II) compound 3, which was unambiguously
determined by multinuclear NMR spectroscopic studies and single
crystal X-ray analysis.
Our present research mainly focus on the preparation of steri-
cally less-demanding chelating silyl ligands, investigation of their
reactive behavior toward transition-metal complexes, and study
of the unique bonding structures and reactivity toward hydrosilane
ligands for the silyl-metal complexes formed by Si–H activation.
We have reported a number of unusual silyl group 10 transition
metal complexes depending on the metals and the structures of
disilylbenzene ligands [4].
2. Experimental
2.1. Materials and equipment
1H, 29Si and 31P NMR spectra were recorded on JEOL LA500 (for
solution NMR). Chemical shifts are given in ppm using external ref-
erences (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 stored over molecular sieves (4 Å). All
⇑
Corresponding author.
E-mail addresses: iamyhli@njupt.edu.cn (S. Wang), iamswang@njupt.edu.cn
(Y.-H. Li).
http://dx.doi.org/10.1016/j.ica.2016.07.024
0020-1693/Ó 2016 Elsevier B.V. All rights reserved.

158
S.-S. Sun et al. / Inorganica Chimica Acta 451 (2016) 157–161
manipulations of air-sensitive materials were carried out under a
nitrogen atmosphere using standard Schlenk tube techniques or
2.2.3. Preparation of {1,2-C6H4(SiMe2)Si(OC6H5)2}PtII(dmpe) complex
(3)
in
a
glove box. 1,2-bis(dimethylphosphino)ethane (Aldrich)
A
mixture of {1,2-C6H4(SiMe2)(SiH2)}PtII(dmpe) (255 mg,
were purchased and used as received, Pt(PEt3)4 and hydrosilane
1,2-C6H4(SiMe2H)(SiH3) were prepared according to the relevant
literature method [4b, 6].
0.5 mmol) and phenol (103 mg, 1.1 mmol) in anhydrous THF
(4 mL) was stirred at room temperature for 3 h under nitrogen,
and then stirred at 50 degree 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, 301 mg (87%). 31P{1H} NMR (THF-d8,
2.2. Synthesis
2
1
202.0 MHz):
d 41.77 (d, JP-P = 13, JPt-P = 1353), 37.31 (d,
1
2JP-P = 13, JPt-P = 1476). 1H NMR (THF-d8, 499.1 MHz): d 0.52 (6H,
2.2.1. Preparation of 1-(dimethylsilyl)-2-silylbenzene complex (1)
To a solution of phenyltris(N,N,N0-trimethylethylenediamino)-
silane (48 g) in hexane (250 mL) was added a pentane solution of
tBuLi (1.53 M, 217 mL) over 40 min at 0 degree under nitrogen.
Afrer stirring at room temperature for 3 h, the solution was added
by using a polyethylene tube to a solution of Me2SiCl2 (195 g) in
hexane (120 mL) at 0 degree over 40 min. After the addition was
completed, the mixture was allowed to warm to room temperature
and then heated at 50 degree for about 4 h. Most of the solvents
and excess of Me2SiCl2 were removed under reduced pressure at
room temperature. After the addition of Me2SiCl2 (20 mL) to the
residue, iPrOH (300 mL) was added dropwise at 0 degree. The mix-
ture was stirred at room temperature for 12 h. Volatiles were
removed under vacuum, hexane (600 mL) was added, and the mix-
ture was filtered through Celite. The filtrate was further filtered
through a short pad of SiO2 (50 g) to remove the remaining salt.
After evaporation, the residue was subjected to bulb-to-bulb distil-
lation to give 34 g (75%) of 1-Dimethyl(isopropoxy)si-lyl-2-(triiso-
propoxysilyl)benzene (oven temperature 150 oC/1 mmHg). 1H
NMR (CDCl3, 300 MHz) d 0.51 (6H, s), 1.23 (18H, d), 1.26 (6H, d),
4.11 (1H, septet), 4.26 (3H, septet), 7.35-7.45 (2H, m), 7.82-7.85
(1H, m), 7.97-8.05 (1H, m).
4
d, JP-H = 3, 3JPt-H = 23, SiMe), 1.22–1.29 (6H, m, PMe), 1.55–1.59
3
(6H, m, PMe), 1.67–1.80 (4H, m, PCH2CH2P), 7.64 (1H, d, JH-H = 7,
3
aromatic-H), 7.39 (1H, d, JH-H = 8, aromatic-H), 7.16 (1H, td,
3
6JP-H = 1, JH-H = 7, aromatic-H), 7.06–7.11 (1H, m, aromatic-H),
6.94–6.99 (3H, m, aromatic-H), 6.85-6.89 (3H, m, aromatic-H),
6.69–6.73 (2H, m, aromatic-H), 6.64–6.68 (2H, m, aromatic-H).
2
29Si{1H} NMR (THF-d8, 99.1 MHz, INEPT): d 29.14 (dd, JP-Si
=
2
1
138 Hz, JP-Si = 10 Hz, JPt-Si = 1119 Hz, SiMe2). Anal. Calcd. for
26H36O2P2PtSi2 (%) (measured after removing the solvent): C,
C
45.01; H, 5.23. Found: C, 45.46; H, 5.58.
2.3. X-ray Crystallography
The diffraction data were collected at 293 K on a Bruker Smart
APEX CCD diffractometer with Mo-Ka radiation (k = 0.71073 Å),
and the data reduction was performed using Bruker SAINT. An
absorption correction was applied using the method of multi-
scans. Unit cell parameters were obtained by a least-squares
analysis.
The structure was solved using direct methods, which yielded
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 param-
eters and included in structure factor calculations in the final stage
of full-matrix least-squares refinement. All calculations were per-
formed using the SHELXTL programs [7]. The bis(silyl) platinum
(II) complexes were relatively more stable than the corresponding
silyl nickel and palladium compounds during data collection at
To an ether suspension (100 mL) of LiAlH4 (10 g) was added
dropwise
a solution of 1-Dimethyl(isopropoxy)silyl-2-(triiso-
propoxysilyl)benzene (34 g) in ether 80 mL at 0 °C over 40 min.
The mixture was stirred for 5 h at room temperature and 7 h at
reflux. GC–MS analysis of the mixture at this stage showed the
presence of partially reduced products. Then, LiAlH4 (1.5 g) was
added and the mixture was refluxed for another 13 h. After
removal of ether under reduced pressure, the remaining mixture
was extracted with hexane (250 mL * 3), and then filtered through
Celite. Hexane was removed under reduced pressure, the product
was transferred to a cold flask under high vacuum. Purification
by distillation gave 9.6 g of 1-(dimethylsilyl)–2-silyl-benzene,
134 0C/50 Torr, as colorless liquid. 1H NMR (CDCl3, 300 MHz): d
0.39 (6H, d), 4.32 (3H, s), 4.66 (1H, septet), 7.35–7.45 (1H, m),
7.32–7.45 (1H, m), 7.59 (1H, dd), 7.68 (1H, dd); 13C NMR (CDCl3,
300 MHz): d ꢀ3.27, 128.57, 129.29, 134.22, 135.40, 137.51, 138.24.
Table 1
Crystallographic data for 3.
Compound
3
Formula
C
28H41O3P2PtSi2
Formula weight
Crystal color
Crystal system
Space group
a (Å)
738.81
Colorless
Monoclinic
P 21/c
9.2193(18)
b (Å)
31.463(6)
c (Å)
11.320(2)
90
105.26(3)
90
(o)
2.2.2. Preparation of {1,2-C6H4(SiMe2)(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 solu-
tion was added hydrosilane (1, 53 mg, 0.32 mmol) at 0 °C, and the
mixture was stirred at 0 °C 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, 147 mg (90%). 1H
NMR (THF-d8, 499.1 MHz): d 0.38 (6H, d, 4JP-H = 3, 3JPt-H = 23, SiMe),
1.51–1.62 (12H, m, PMe), 1.67–1.82 (4H, m, PCH2CH2P), 5.53 (2H, t,
a
b (o)
c
(o)
Volume (Å3)
3167.7(11)
Z
4
T (K)
293(2)
1.549
1476
4.632
Dx (Mg mꢀ3
F(0 0 0)
)
l
(mmꢀ1
)
h range for data collection (°)
Index ranges
Measured reflections
Independent reflections
Data/restraints/parameters
Rint
Reflections with I > 2
R1 [I > 2 (I)]
wR2 (all data)
1.29–24.98
ꢀ10 6 h 6 10, ꢀ36 6 k 6 37, ꢀ10 6 l 6 13
16,506
5547
5547/0/332
0.027
4664
0.025
0.051
1
2
3JP-H = 7, JSi-H = 159, JPt-H = 22, SiH2), 7.01–7.07 (2H, m), 7.45 (1H,
r(I)
d, J = 7), 7.58 (1H, d, J = 7). 31P{1H} NMR (THF-d8, 202.0 MHz): d
r
2
39.5 (d, JP-P = 13, 1JPt-P = 1623), 40.0 (d, 2JP-P = 13, 1JPt-P = 1337).

S.-S. Sun et al. / Inorganica Chimica Acta 451 (2016) 157–161
159
Table 2
by the reductive elimination of dihydrogen. Most of the similar
mononuclear bis(silyl) platinum(II) complexes bearing
Selected bond lengths (Å) and selected bond angles (°) for 3.
organophosphorus ligands with low steric hindrance can be easily
converted to the corresponding dinuclear platinum complexes
with the bridging silylene by intermolecular dimerization. Our pre-
vious studies have shown that the NMR spectra in THF-d8 showed
the formation of bis(silyl) platinum(II) complex 2 as a major pro-
duct together with a small quantity of 4 (Scheme 2, 2/4 = ca.
95/5 by 1H and 31P{1H} NMR integrations in THF-d8). Dinuclear
complex 4 is a dimer of 2, and 2 and 4 have proved to be in equi-
librium in solution [4e].
Pt1-Si1
Pt1-P1
Si2-O1
Si1-Pt1-Si2
P1-Pt1-Si2
P2-Pt1-Si1
Pt1-P1-C23
O1-Si2-O2
O2-Si2-Pt1
2.3650(10)
2.3199(12)
1.685(3)
Pt1-Si2
Pt1-P2
Si2-O2
P1-Pt1-P2
P2-Pt1-Si2
Si1-Pt1-P1
Pt1-P2-C24
Si2-O2-C15
C3-Si1-Pt1
2.3193(12)
2.3067(10)
1.685(2)
85.25(4)
93.96(4)
97.86(4)
107.64(16)
125.4(2)
82.91(4)
175.63(4)
176.87(4)
106.92(17)
94.39(12)
117.54(10)
110.04(12)
The mononuclear bis(silyl) platinum(II) complexes bearing a
chelating dmpe (dmpe = Me2PCH2CH2PMe2) or depe (depe = Et2-
PCH2CH2PEt2) ligand derived from this chelating disilyl ligand are
difficult to be trapped as crystals. Despite the high concentration
of the major product 2, recrystallization of the product mixture
from THF or toluene afforded only crystals of 4. Single crystal
X-ray analysis unambiguously confirmed the structure of 4.
Although silyl compound 2 could not be obtained as a crystal, 2
can be trapped by two phenol molecules in view of its unique reac-
tivity towards sterically unhindered alcohol. The Si-H bonds in the
SiH2 moiety of the similar silyl palladium and nickel complexes do
not have such a unique reactivity [4a, 4h]. Addition of excess
phenol to a mixture of 2/4 in THF afforded an unusual diphenoxy
substituted silyl platinum(II) compound 3 (Scheme 3). Although
the mechanism for the formation of complex 3 is not clear, the
room temperature. The crystallographic data are summarized in
Table 1 and selected geometric parameters are listed in Table 2.
3. Results and discussion
We have studied the reaction of a chelating hydrosilane, 1,2-bis
(silyl)benzene, which has a trihydrosilyl group, with group 10 tran-
sition-metal complex. Silane 1, 1-(dimethylsilyl)-2-silylbenzene
(Scheme 1) has high reactivity toward platinum complex Pt
(dmpe)(PEt3)2 in toluene at room temperature in the ratio of 1:1
to afford the bis(silyl) platinum(II) complex 2 bearing a chelating
dmpe ligand in high yield (Scheme 2). The whole reaction process
underwent the successive oxidative addition of the Si–H bond to
the Pt(0) center and dissociation of PEt3 molecules accompanied
Scheme 1. Synthesis of 1-(dimethylsilyl)-2-silylbenzene complex 1.
Scheme 2. Synthesis of the mononuclear complex {1,2-C6H4(SiMe2)(SiH2)}PtII (dmpe) (2).

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S.-S. Sun et al. / Inorganica Chimica Acta 451 (2016) 157–161
Scheme 3. Synthesis of the novel di-phenoxy substituted silyl platinum(II) compound 3.
formation of complex 3 may be explained by a sequence of
oxidative addition of the O-H and Si–H bonds to the Pt center,
followed by Si-O coupling accompanied by the reductive
elimination of dihydrogen. Compounds 2 and 3 are the very rare
examples of silyl transition-metal complexes derived from this
chelating hydrosilane ligand. To the best of our knowledge, there
are only 7 examples of bis(silyl) metal complexes prepared from
this ligand registered in the Cambridge Structural Database,
(4)o bond angles respectively. The average bond lengths of Pt-Si
(2.3193(12)-2.3650(10) Å) and Pt-P (2.3067(10)–2.3199(12) Å)
are in good agreement with those observed in other similar com-
plexes [4]. The bond angles of P1-Pt1-Si2 and P2-Pt1-Si1 are
175.63(4)° and 176.87(4)° respectively, showing the Pt atom is
slightly deviated from the P2Si2 plane, which can be attributed to
the steric repulsion between the substituent groups on the silyl
and phosphorus ligands. Furthermore, four atoms (P1, C23, C24
and P2) are not on the same plane. The plane bounded by P1,
C23 and C24 makes a dihedral angle of 42.83° to the plane C23-
C24-P2. The two phenyl rings are situated in cis-position of the
plane bounded by O1-Si2-O2 (Table 2).
among them, only
presented.
6 bis(silyl) platinum(II) compounds are
Crystals of 3 suitable for single-crystal X-ray analysis were
grown by cooling a dimethoxyethane solution to 0 °C, and the
molecular structure determined at 293 K was unambiguously con-
firmed by single-crystal X-ray structure analysis (Fig. 1). Complex 3
crystallizes in the monoclinic space group P 21/c with 0.5 molecule
of solvent of dimethoxyethane (Table 1). The central Pt atom in
diphenoxy substituted silyl compound 3, which is surrounded by
two chelating P atoms and two chelating Si atoms from one
hydrosilane ligand adopts a distorted square-planar P2Si2Pt(II)
coordination geometry with P1-Pt1-P2 = 85.25(4)°, P2-Pt1-
Si1 = 176.87(4)°, P1-Pt1-Si2 = 175.63(4)°, and P2-Pt1-Si2 = 93.96
The structure of complex 3 was also well identified by multin-
uclear NMR spectroscopic studies. In the 31P{1H} NMR spectrum,
the two chemically inequivalent phosphorus atoms give rise to a
1
pair of doublets with relatively moderate JPt-P values which are
within the typical range of those observed in cis-bis(silyl)bis(phos-
phine)platinum(II) complexes [8]. The signals for P-P coupling with
small 2JP-P values in the spectrum suggest that both P atoms are in
cis-position. P-H signals for Si(CH3)2 groups of complex 3 in which
the hydrogen atoms on the two methyl groups are chemically
equivalent appear as a doublet in the 1H NMR spectrum, which
suggests that one P atom is trans and the other P atom is cis to
the Si(CH3)2 unit. Signals for SiMe2 groups in the proton-decoupled
29Si NMR spectrum are also consistent with the structure. The
SiMe2 signals (a doublet of doublets) with a large (138 Hz) and a
2
small (10 Hz) JP-Si values, indicate that the SiMe2 group is in cis-
position relative to one P atom and trans to the other P atom.
4. Conclusion
In this contribution, an unusual diphenoxy substituted (bis)silyl
platinum(II) complex 3 bearing a chelating dmpe ligand by succes-
sive oxidative addition, reductive elimination and dehydrocou-
pling reaction of a kind of poly(silyl) chelating hydrosilane has
been established. We report the synthesis and rarity of the molec-
ular structure of this new complex which is one of the very few
examples of bis(silyl) platinum(II) complexes derived from this
chelating hydrosilane ligand registered in the Cambridge Struc-
Fig. 1. The structure of 3 (thermal ellipsoids are at the 30% probability level).
Hydrogen atoms bound to carbon atoms are omitted for clarity.

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Acknowledgments
This work was financially supported by the National Key Basic
Research Program of China (Grant No. 2014CB648300), the
National Natural Science Foundation of China (Grant No.
51173082 and 51274159), the Natural Science Foundation of
Jiangsu Province (BK20141425), the Natural Science Foundation
of Colleges and Universities in Jiangsu Province (13KJB150028),
the Priority Academic Program Development (PAPD) of Jiangsu
Higher Education Institutions and the Ministry of Education of
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Crystallographic data for the structure has been deposited with
the Cambridge Crystallographic Data Centre, CCDC-1439490 for
the complex 3. Copies of the data can be obtained free of charge
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ccdc.cam.ac.uk/datarequest/cif, e-mail for deposition: deposit@
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