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Some New Mixed-Substituent Phosphazenes Derived from N-Silylphosphoranimines

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Abstract

A series of mixed-substituent P-alkyl-N-silylphosphoranimines, Me3SiN=P(R)XY (R = n-Pr, n-Bu, i-Pr; X, Y = Br, OCH2CF3, OPh), were studied as possible precursors to cyclic and/or polymeric phosphazenes. Three synthetic methods were investigated: sealed-ampule thermolysis, dynamic-vacuum thermolysis, and reactions with CF3CH2OH. While the results varied with the specific precursor and reaction conditions employed, these synthetic methods afforded a variety of new non-geminally substituted cyclic trimers, [N=P(R)X]3 (R = n-Pr, n-Bu, i-Pr; X = Br, OCH2CF3, OPh), one new polymer, [N=P(n-Pr)OPh] n , and a simple route to a known polymer, [N=P(Ph)OCH2CF3] n . The trimers were generally obtained as mixtures of cis and trans isomers although, in one case, [N=P(i-Pr)OPh]3, the pure trans isomer was isolated and structurally characterized by X-ray diffraction.

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Acknowledgments

We thank the Robert A. Welch Foundation (Grant P-0759) and the TCU Research Fund for financial support of this work. The X-ray diffraction analysis was performed by William H. Watson and Satish Bodige, Texas Christian University.

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Authors and Affiliations

  1. Department of Chemistry, Texas Christian University, Fort Worth, TX, 76129, USA

    Robert H. Neilson

  2. Idaho National Engineering and Environmental Laboratory, P.O. Box 1625, Idaho Falls, ID, 83415, USA

    John R. Klaehn

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  1. Robert H. Neilson
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  2. John R. Klaehn
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Correspondence to Robert H. Neilson.

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This paper is dedicated to Professor Harry R. Allcock in honor of his pioneering research and his steadfast leadership in the field of inorganic polymer chemistry.

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Neilson, R.H., Klaehn, J.R. Some New Mixed-Substituent Phosphazenes Derived from N-Silylphosphoranimines. J Inorg Organomet Polym 16, 319–326 (2006). https://doi.org/10.1007/s10904-006-9067-2

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