Chemical transformations of functional polycarbosilanes |
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Authors: | Robert J P Corriu William E Douglas Elisabeth Layher and Ravi Shankar |
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Affiliation: | (1) Unité Mixte CNRS/Rhône-Poulenc/UM II, CNRS UM 44, Université de Montpellier II Sciences et Techniques du Languedoc, Place E. Bataillon, 34095 Montpellier Cédex 5, France |
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Abstract: | The functional polycarbosilane Si(X
2)C2H4]
n
, whereX
2=Cl2 (1), was chemically transformed into the corresponding polymers, whereX
2=F2 (3), (2-N, N-dimethylbenzylamino)(H) (5), (9-N,N-dimethyl-1-naphthylamino)(H) (6), (1-C10H7)(H) (7), Me2 (8a), (Me3SiNH)2 (10), and (vinyl)(H) (11). The functional polycarbosilane, whereX
2=H2 (2), was converted into the polymers, whereX
2=Me(H) (8b) and (OMe)2 (9). Reaction of3 with KF in the presence of 18-crown-6 gave rise to the poycarbosilane4 containing both pentacoordinate and tetracoordinate silicons in the proportion of 1:15 as shown by quantitative19F and29Si NMR. Conversion of a greater proportion of silicon atoms to the pentacoordinate state was not possible because of insolubility of the resulting ionomer in the reaction medium. |
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Keywords: | Polycarbosilane silicon pentacoordinate hypervalent |
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