Synthesis of polysilanes bearing pendant carbosilyl groups and 29Si-NMR probe on the tacticity using side chain silicon atoms

Abstract

New functional polysilanes [R2R1Si(CH2)2SiH]n (R=Me, R1=H (1); R=R1=Et (2); R=Me, R1=Ph (3)) bearing carbosilyl side chains have been synthesized by catalytic dehydropolymerization of precursor carbosilanes R2R1SiCH2CH2SiH3 using Cp2TiCl2–BuLi as a catalyst. These polymers are characterized by 1H, 13C, 29Si, {1H–29Si} HSQC NMR spectroscopy, GPC and TGA. Attempts to delineate the tacticity from the analysis of deconvoluted 29Si{1H}-NMR signals associated with the side chain silicon atoms reveal that the triad concentration ratio follows a Bernoullian statistical model for polymers 1 and 2 only.