Reactions and mechanisms of chloroplatinic acid hexahydrate with dimethyldi(4-N,N-dimethylaminophenyl)silane

Article abstract of DOI:10.1016/j.inoche.2011.03.063

The reaction of dimethyldi(4-N,N-dimethylaminophenyl)silane (1) and chloroplatinic acid hexahydrate was carried out in acetone (ace). A complex salt, [H(dma)]₂(PtCl₆)·0.5ace (2·0.5ace) (dma = N,N-dimethylphenylamine), was obtained and characterized by Single-crystal X-ray diffraction. At the same time, byproducts (4-dimethylaminophenyl)dimethylsilanol (3), dma, 4-(dimethylphenyl silyl)-N,N- dimethylaniline (4), and 1,3-Bis(4-(dimethylamino)phenyl)-1,1,3,3-tetra- methyldi- siloxane (5), structurally confirmed by FT-IR, ¹H NMR, ¹³C NMR, ²⁹Si and ESI MS NMR spectra, were found. This indicates that the cleavages of Si-C and C-N bonds of 1 in the reaction occurred. In addition, the reaction mechanisms were referred.

Full text of DOI:10.1016/j.inoche.2011.03.063

Inorganic Chemistry Communications 14 (2011) 1027–1031
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Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Reactions and mechanisms of chloroplatinic acid hexahydrate with
dimethyldi(4-N,N-dimethylaminophenyl)silane
⁎
Peng Wang, Zheng Yue, Jie Zhang, Shengyu Feng
Key Laboratory of Special Functional Aggregated Materials, Ministry of Education School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of dimethyldi(4-N,N-dimethylaminophenyl)silane (1) and chloroplatinic acid hexahydrate was
carried out in acetone (ace). A complex salt, [H(dma)]2(PtCl6)·0.5ace (2·0.5ace) (dma=N,N-dimethylphe-
nylamine), was obtained and characterized by Single-crystal X-ray diffraction. At the same time, byproducts
(4-dimethylaminophenyl)dimethylsilanol (3), dma, 4-(dimethylphenyl silyl)-N,N- dimethylaniline (4), and
1,3-Bis(4-(dimethylamino)phenyl)-1,1,3,3-tetra-methyldi- siloxane (5), structurally confirmed by FT-IR, 1H
NMR, 13C NMR, 29Si and ESI MS NMR spectra, were found. This indicates that the cleavages of Si–C and C–N
bonds of 1 in the reaction occurred. In addition, the reaction mechanisms were referred.
© 2011 Elsevier B.V. All rights reserved.
Received 14 February 2011
Accepted 31 March 2011
Available online 7 April 2011
Keywords:
Dimethyldi(4-N,N-dimethylaminophenyl)
silane
Chloroplatinic acid hexahydrate
Si–C bond cleavage
C–N bond cleavage
σ-complex
Hydrosilylation of multiple bonds, in particular to C=C or C≡C
bonds, is one of the most important reactions in organosilicon
chemistry. Such reaction was widely applied for synthesizing novel
functional silanes and obtaining new silicon-based materials com-
posed of polymers or dendrimers [1,2]. Among various catalysts
proposed for the hydrosilylation, H2PtCl6 (for example, Speier's
catalyst) has been most commonly used in the synthesis of
polycarbonsilanes [3]. An activation of the Speier catalyst by addition
of a base (e. g. sodium carbonate) was reported [4]. Moreover, poorly
nucleophilic amines (e. g. aniline, hexamethyldisilazane) [5] and
sterically hindered amines (such as N,N-dimethylphenylamine) [6]
were reported to induce higher reaction rates, decrease side reactions,
and reduce catalyst consumption. The promotion mechanism may
include two reasons: one is the coordination effect; the other is
neutralization effect [2].
The platinum-coordinated compounds based on primary amines
and secondary amines have been reported, and the coordination effect
is dominative between platinum salts and such amines [7]. How about
tertiary amine? Which effect will occur in chloroplatinic acid-
including catalysis systems using tertiary amines as assistant? So we
investigated the reaction of dimethyldi(4-N,N-dimethylaminophenyl)
silane (1) and chloroplatinic acid hexahydrate in acetone, expecting
to obtain a silicon bridge-containing platinum-amine coordination
compound (Scheme 1).
over, the products including (4-dimethylaminophenyl)dimethylsilanol
(3), N,N-dimethylphenylamine (dma), 4-(dimethylphenylsilyl)-N,N-
dimethylaniline (4), and 1,3-Bis(4-(dimethyl-amino)-phenyl)-1,1,3,3-
tetramethyldisiloxane (5) were also found. It indicates that cleavages of
Si–C and C–N bonds of 1 occurred in the reaction.
The cleavage of Si–C bonds in arylsilanes has been investigated for
over a century [8]. And such reaction has been widely used to
synthesize new organosilicon compounds [9], produce C–OH func-
tional group particularly in the synthesis of optic reactive compounds
[10–13], and study the effect factors of silane coupling agents on sol–
gel reactions [14]. There are many reagents utilized in cleaving the Si–
C bonds, such as anhydrous HCl in glacial acetic acid [15], potassium
amide in liquid ammonia [16], elemental lithium [17], and samarium-
catalyst [9]. However, to our best knowledge, no study regarding to
the cleavage of Si–C bond in common organic solvents such as acetone
in this study has been reported to date. Therefore, the cleavage
mechanism will also be discussed in detail.
Some single crystals of complex salt 2·0.5ace were obtained
unexpectedly in the reaction of 1 [18,19] and chloroplatinic acid
hexahydrate with diffusion method in H-shaped tube. However, when
acetone solutions of 1 and chloroplatinic acid hexahydrate were mixed
Unexpectedly, a complex salt, [H(dma)]2(PtCl6)·0.5ace (2·0.5ace)
(dma=N,N-dimethylphenylamine; ace=acetone) was obtained. More-
⁎
Corresponding author. Tel.: +86 531 8836 4866; fax: +86 531 8856 4464.
E-mail address: fsy@sdu.edu.cn (S. Feng).
Scheme 1. Silicon bridge-containing platinum-amine coordination compound.
1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2011.03.063

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P. Wang et al. / Inorganic Chemistry Communications 14 (2011) 1027–1031
Fig. 1. Molecular structure of 2·0.5ace, showing displacement ellipsoids at 30% probability for non-H atoms.
directly, not crystals but powders were obtained. It indicates that
diffusion method may avoid impetuous reactions and allow gradual
formation of defined crystals [20]. In addition, the byproducts including
3, 4, dma, and 5 were obtained in the solution. For comparison, pure
compound 5 was prepared through hydrolyzation of chlorosilane using
ZnO as acid-absorbent (see support information).
As shown in the stacking picture (Fig. 2), crystal structure of
2·0.5ace reveals two PtCl6 units, one acetone molecule, and four
protonated N,N-dimethylanline units in a cell. This provides a
combination type in the 2·0.5ace where anions and cations are
staggered with respect to each other. In addition, two types of
hydrogen bonds were found in the crystal structure, namely N–H…
Cl–Pt and C–H…Cl–Pt hydrogen bonds. The former was assigned to
the formation of bifurcated N–H…Cl2Pt hydrogen bond (B-2)
reported [23] in inorganic supramolecular synthons during the
construction of zigzag assemblies in the solid state. Such bonding is
facilitated by the interaction between a strong hydrogen donor (H
from N–H) and an electronegative atom acceptor (Cl from Cl–Pt).
The hydrogen bond length of H…Cl from N–H…Cl–Pt hydrogen
bond was found to be 2.620 or 2.766 Å, agreeing well with the
bond lengths observed in N-H…Cl–M (M=Zn or Cu) reported
previously [24,25]. In addition, two types of 1-D H-bond self-
assembly zigzag chains were found crosslinked with the Pt atoms,
which assembled themselves into 2-D sheets. According to the
crystal structure of 2·0.5ace, no coordination effect was found
between the tertiary amine and chloroplatinic acid. Instead, the
complex salt forms based on the neutralization effect.
Fig. 3 shows the FT-IR spectra of 1 (A) and byproducts (B) in
solution. Peaks at 1125 cm−1 and 1599 cm−1 that correspond to the
stretching vibrations of Si–C and C=C bonds from Si–Ph function,
are found much weaker in spectrum B than that in spectrum A. It
indicates that part Si–C bonds of Si–Ph cleaved during the reaction.
On the other hand, a peak at 3080 cm−1, attributed to the stretching
vibration of C–H bond in benzene ring, was observable in spectrum
A but unconspicuous in spectrum B. It further establishes the
cleavage of Si–C bonds of Si–Ph. The two new peaks found in
spectrum B, at 3385 cm−1 and 1067 cm−1, are attributed to the
Results obtained from Single-crystal X-ray diffraction indicate that
compound 2·0.5ace crystallizes in space group P21/n (Fig.1). The
structure data was compiled in Table 1. Each Pt(IV) atom shows
octahedral coordination geometry in the equatorial positions, which is
coordinated by six chlorine atoms, displaying an almost regular
octahedron structure (Pt–Cl distances in the range from 2.323(4) to
2.326(2) Å). All Cl–Pt–Cl angles range from 88.57(6)° to 90.63(6)° are
detailed in Table 2. The closest Pt–N distance is 4.331(7) Å, which is
much longer than the normal Pt–N coordinated bond length (~2.0 Å)
[21]. In addition, the bond length of C1–N1 is 1.449(6) Å, which is
longer than bond length observed from 2-(4-cyanophenyl)-2-(4′-
(dimethylamino)phenyl)propane (1C) (1.393(5) Å). The measured
torsion angle of C7-N-C1-C2 is about 111.52(4)° while the analogous
angle in 1C is 170.4(3)° [22]. It indicates that the N-methyl is not
coplanar with the benzene ring that can be found in the quinonoid
structures of dma and 1C. Another reason may be the protonation of
amino group, which may interrupt the conjunction between the
amino group and the benzene ring.
Table 1
Crystallographic data for 2·0.5ace.
2·0.5ace
Empirical formula
C17.50H27Cl6N2O0.50Pt
Fw
681.20
cryst syst
space group
monoclinic
P21/n
Table 2
a, Å
b, Å
c, Å
α, deg
11.8196(15)
8.3007(11)
14.9146(19)
90.00
Selected bond distances (Å) and angles (degree) of 2·0.5ace in Fig. 1.
Distances
Angles
β, deg
109.544(2)
90.00
1379.0(3)
2
1.641
3123
2481
0.0312
27.59
0.0391
C1–N1
C7–N1
Pt–Cl1
Pt–Cl2
Pt–Cl3
1.449(6)
1.498(8)
2.323(4)
2.326(2)
2.326(1)
4.700(8)
1.51(1)
1.511(1)
1.245(1)
4.331(7)
C1–N1–C7
C7–N1–C8
Cl1–Pt–Cl2
Cl2–Pt–Cl3
111.5(5)
112.5(7)
90.63(6)
88.57(6)
90.16(7)
105.3
129.3
125.4
111.52 (4)
γ, deg
V, Å3
Z
Dc. g cm−3
Cl1–Pt–Cl3
No. of rflns collected
No. of unique data
Rint
C4–Pt
C01–C03–C02
C01–C03–O01
C02–C03–O01
C7–N–C1–C2
C01–C03
C02–C03
C03–O01
Pt–N1
θmax, deg
a
R1 (IN2σ(I))
wR2(all data)
0.1130
a
Selected nearest distance of Pt–N.

P. Wang et al. / Inorganic Chemistry Communications 14 (2011) 1027–1031
1029
Fig. 2. The crystal structure stacking picture of 2·0.5ace, showing layers comprising zigzag chains based upon N−H…Cl2Pt and C−H…Cl−Pt hydrogen bonds. Synthon B-2:
H…Cl, 2.620, 2.766 Å; N−H…Cl, 141.7, 144.1°; H…Cl−Pt, 85.4, 88.8°; Cl…H…Cl, 74.1°; and crosslinked by C−H…Cl−Pt hydrogen bond: H…Cl, 2.866 Å; C−H…Cl, 148.7°; H…Cl−
Pt, 93.0°.
vibration of Si–OH in 3 and the vibration of Si–O–Si bond of 5 (see
Fig. S1), respectively.
to the silicon atom presented in 1, and the latter two were assigned to
the silicon atoms found in 3 and 4, respectively. Although the
vibration of Si–O–Si bond of 5 was detected by IR spectra, NMR signals
for silicon atoms in 5 (See Fig. S5) were not noticeable due to its low
quantity.
Fig. 4 presents an ESI Mass Spectra (MS) of the mother liquor
obtained from the reaction of 1 and chloroplatinic acid. Intense peaks
at 196.11, 255.19, 299.19, and 372.24 were used as calculated values
for [H·3]+ (196.11), [4]+ (255.14), [H·1]+ (299.19), and [5]+
(372.21), indicating the presence of 3, 4 and 5 in the solution.
As proposed, chloroplatinic acid hexahydrate ionizes as acid in
acetone, providing acidic conditions for the cleavage of Si–C bond
(Scheme 2). Theoretically speaking, the cleavage reaction of 1
involves the formation of σ-complex in acidic condition, as reported
recently [14]. The stability of σ-complex is one of the effect factors
that govern the bond cleavage. Also, the electron donor ability of
dimethylamino group in 1 can provide extra stability. These can
In order to make an intensive study, d6-acetone was used instead
of acetone for NMR characterization (Fig. S2). 1H NMR spectra of 1 (I)
and products (II) show that the chemical shifts of H from N-Me
function in both spectra are virtually similar. However, the chemical
shifts of H atoms on benzene ring in the two spectra are found
differently; this may be due to an environmental shifting of benzene
ring when Si–C bond was cleaved. In addition, most of the H from
Si–Me function shift to a higher field, which suggested the formation
of Si–OH and Si–O–Si functions (See Fig. S3). Figure S2B shows the 13
C
NMR of 1 (I) and products (II). The corresponding data of them and
possible compounds were compiled in Table 3. Noticeably, the
chemical shift at 123.8 ppm that corresponds to the α-C of Si–Ph
was not observed in the spectrum of the byproducts. Nonetheless,
some new peaks at 128.9 ppm were found. In the 29Si-NMR spectra of
1 (I) and products (II) shown in Fig.S2C, one peak at –10.5 ppm was
observed in Fig. S2 (CI) while two different peaks were found at
−6.5 ppm and −13.9 ppm (Fig. S2 (CII)). The former was attributed
Table 3
Comparison of peaks (ppm) in 13C NMR spectra of byproducts (m) and pure products.
Chemical shift
m
150.6
151.5
135.4 134.5 129.8 129.3 118.0 113.8 41.9
0.22
129.2 115.2 112.7 40.8 −0.33
112.6 40.1 −2.10
1
151.9
151.4
135.7
124.4
124.4
112.6 40.1 −1.75
111.8 40.2 0.02
3a
4b
5
134.2
151.3 139.4 135.3 134.2 128.8 127.7 123.1 112.0 40.2 −2.0
152.2
134.8
125.6
112.4 40.1
1.06
dmac 150.7
129.0 116.7 112.7 40.5
a
Values obtained from the data in S. E. Denmark, R. C. Smith, W. T. Chang, J. M.
Muhuhi, J. Am. Chem. Soc. 131 (2009) 3104–3118.
b
Values taken from the data in ref. 14.
c
Values taken from the data in Aldrich Library of 13C and 1H FT NMR Spectra, 2
Fig. 3. The FI-IR spectra of 1 (top) and byproducts in solution (bottom).
(1992) 454 C.

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P. Wang et al. / Inorganic Chemistry Communications 14 (2011) 1027–1031
Fig. 4. ESI mass spectrum of mother liquor upon removing crystals of 2·0.5ace. The inset shows the calculated fits for the four most intense peaks, [4]+, [H·3]+, [H·1]+, and
[5]+
.
interpret the mechanism of Si–C bond cleavage, in which the nitrogen
atom behaves as an internal electron donor group [26] and provides
resonance structures with negatively charged carbon atoms at the o-
and p-positions of the benzene ring. In the presence of water from
chloroplatinic acid hexahydrate, compounds 3 and dma were
obtained from the hydrolysis of σ-complex (A). Meanwhile, com-
pound 3 was partly condensed into 5 while dma was captured by the
chloroplatinic acid to form complex salt 2·0.5ace. Concurrently, the
proton at α-C of silicon atom can migrate reversibly to the p-position
of the benzene ring to give the formation of σ-complex (B). As a result,
compound 4 was obtained, which can be seen as a product of simple
decomposition of C–N bond in the σ-complex (B). Such product is
different from the C–N bond cleavage products including a secondary
amine and a primary alcohol which are obtained through the
hydrolysis of a tertiary amine [27]. Byproduct N-methylenemethana-
mine (6) is a volatile molecule [28], which can't be detected by such
tests. Taken together, the cleavages of Si–C and C–N bonds in 1 are
facilitated by chloroplatinic acid hexahydrate, and a novel complex
salt 2·0.5ace is obtained by the reaction of chloroplatinic acid and
dma based on neutralization effect in acetone.
respect to each other. It is proved that the neutralization effect
between tertiary amine and chloroplatic acid is dominative. Such
conclusion can provide the new insight to design and study the new
catalysis systems for hydrosilylation. Also, Si–C and C–N bond
cleavage reactions of 1 occurred when coexisting with chloroplatic
acid hexahydrate which serves as both catalyst and reactant. Such
reaction mechanisms, including the formation of σ-complexes,
hydrolysis, simple decomposition, and intensive condensation, were
proposed. It shows the possibility of the Si–C bond cleavage in
common organic solvents.
Acknowledgements
The project is financially supported by the National Natural
Science Foundation of China (No. 20874057) and the Key Natural
Science Foundation of Shandong Province of China (No. Z2007B02).
The authors also thank Ms. Siow-Feng Chong for her careful and
critical reading of the manuscript.
In summary, reaction of dimethyldi(4-N,N-dimethylaminophenyl)
silane (1) and chloroplatinic acid hexahydrate in acetone was studied.
[H(dma)]2(PtCl6)·0.5ace (2·0.5ace), (4-dimethylaminophenyl)
dimethylsilanol (3), N,N-dimethylphenylamine (dma), 4-(dimethyl-
phenylsilyl)-N,N-dimethylaniline (4), and 1,3-bis(4-(dimethyla-
mino)-phenyl)-1,1,3,3-tetramethyldisiloxane (5) were found as the
products. Product 2·0.5ace was characterized by single-crystal X-ray
diffraction. Its supramolecular structure was built through the
hydrogen bond self-assembly, with a combination type in the
molecule structure where anions and cations are staggered with
Appendix A. Supplementary material
Crystallographic data (excluding structure factors) for the structures
reported have been deposited with the Cambridge Crystallographic
Data Center as supplementary publication no. CCDC-785611 for
2·0.5ace, and can be obtained free of charge on application to the
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK. [Fax: (Internet.) C44-
1223/336-033; e-mail: deposit@ccdc.cam.ac.uk]. Supplementary data
to this article can be found online at doi:10.1016/j.inoche.2011.03.063.

P. Wang et al. / Inorganic Chemistry Communications 14 (2011) 1027–1031
1031
Scheme 2. Proposed reaction mechanisms.
[17] C. Daschlein, C. Strohmann, Si–C bond activation in the reaction of first generation
Grubbs' catalyst with alkynylsilanes formation of [Cl2{P(C6H11)3}2Ru
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