Synthesis of a novel fumed silica-supported poly-4-oxa-6,7-bis(diphenylarsino)heptylsiloxane platinum complex and its catalytic behavior in the hydrosilylation of olefins with triethoxysilane

doi:10.1016/j.reactfunctpolym.2007.01.006

Reactive and Functional Polymers

Volume 67, Issue 4, April 2007, Pages 294-298

https://doi.org/10.1016/j.reactfunctpolym.2007.01.006 Get rights and content

Abstract

A novel fumed silica-supported poly-4-oxa-6,7-bis(diphenylarsino)heptylsiloxane platinum complex was prepared by treatment of poly-4-oxa-6,7-dichloroheptylsiloxane with potassium diphenylarsenide in THF and then reaction with potassium chloroplatinite. It was found that the title complex is an efficient catalyst for hydrosilylation of olefins with triethoxysilane. The polymeric platinum catalyst is stable and can be reused several times without noticeable loss of activity.

Introduction

Polymer-supported organotransition metal complexes catalysts have the advantages of both homogeneous and heterogeneous catalyzed processes and are currently attracting great interest [1], [2]. These ‘third generation’ catalysts [1], [3] have received much attention [4], [5], [6], [7], [8], [9], [10], [11], [12], [13], [14]. In the preparation of supported catalysts a wide variety of support materials have been used including cross-linked polymer [9], [13], [14], [15], [16], silica [10], [11], [12], and high surface area glasses [17]. Inorganic supports possess a rigid structure which is not deformed by solvent swelling during catalytic reactions. Functionalized polysiloxane grafted on fumed silica is a better support because they have large surface area, high mechanical strength, heat and chemical stability. Polysiloxane grafted on fumed silica-supported sulfur platinum [18], [19], [20], [21], phosphine platinum [22] complexes have been proved to be efficient catalysts for hydrosilylation of olefins with triethoxysilane.

Study of new types of polymer-bound platinum complexes catalysts which might be suitable for hydrosilylation of olefins with triethoxysilane has theoretical and practical significance. Recently, Chen et al. described the synthesis of polysiloxane-supported ferrocenyl selenoether platinum complexes and their catalytic behavior in the hydrosilylation of olefins with triethoxysilane [23]. However, to the best of our knowledge, no hydrosilylation of olefins with triethoxysilane catalyzed by a fumed silica-supported bidentate arsine platinum complex has been reported until now. In this paper, we wish to report the synthesis of a fumed silica-supported poly-4-oxa-6,7-bis(diphenylarsino)heptylsiloxane platinum complex (abbreviation: ‘Si’–2As–Pt) and its catalytic properties in the hydrosilylation of olefins with triethoxysilane. The novel polymeric bidentate arsine platinum complex could be easily prepared by treatment of poly-4-oxa-6,7-dichloroheptylsiloxane with potassium diphenylarsenide in THF and then reaction with potassium chloroplatinite in acetone (Scheme 1).

Section snippets

Experimental

All hydrosilylation products were characterized by comparison of their spectra and physical data with authentic samples. IR spectra were obtained using a Perkin–Elmer 683 instrument. ¹H NMR spectra were recorded on a JEOL FX-90Q (90 MHz) or a Bruker AC-P400 (400 MHz) spectrometer with TMS as an internal standard in CDCl₃ as solvent. Microanalyses were obtained using a Perkin–Elmer 240 elemental analyzer. X-ray photoelectron spectroscopy (XPS) spectra were obtained using a KRATOS XSAM 800 electron

Results and discussion

A novel fumed silica-supported poly-4-oxa-6,7-bis(diphenylarsino)heptylsiloxane platinum complex (abbreviation: ‘Si’–2As–Pt ) was conveniently prepared by treatment of poly-4-oxa-6,7-dichloroheptylsiloxane with potassium diphenylarsenide in THF and then reaction with potassium chloroplatinite in acetone (Scheme 1). A percentage conversion of 77% was obtained in the transformation of ‘Si’–2Cl to ‘Si’–2As according to the elemental analyses. The polymer-bound platinum complexes catalysts are very

Conclusion

We have described a novel fumed silica-supported bidentate arsine platinum complex whose preparation is simple and convenient. This complex has not only high activity for hydrosilylation of olefins with triethoxysilane, but offers practical advantages such as easy handling, separation from the product and reuse.

Acknowledgement

This work was supported by the Natural Science Foundation of Jiangxi Province in China (Project No. 0420015).

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Synthesis of a novel fumed silica-supported poly-4-oxa-6,7-bis(diphenylarsino)heptylsiloxane platinum complex and its catalytic behavior in the hydrosilylation of olefins with triethoxysilane

Abstract

Introduction

Section snippets

Experimental

Results and discussion

Conclusion

Acknowledgement

J. Organomet. Chem.

J. Mol. Catal.

J. Mol. Catal.

React. Funct. Polym.

Catal. Commun.

J. Mol. Catal. A: Chem.

J. Mol. Catal. A: Chem.

J. Organomet. Chem.

J. Mol. Catal.

J. Organomet. Chem.

J. Organomet. Chem.

Adv. Organomet. Chem.