American Chemical Society
om301052f_si_002.cif (18.27 kB)

Nickel-Catalyzed Cyclopolymerization of Hexyl- and Phenylsilanes

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posted on 2013-02-25, 00:00 authored by Makoto Tanabe, Atsushi Takahashi, Tomoko Fukuta, Kohtaro Osakada
[Ni­(dmpe)2] (dmpe = 1,2-bis­(dimethylphosphino)­ethane) catalyzed the dehydrogenative polymerization of hexylsilane in toluene at room temperature to produce a mixture of acyclic and cyclic poly­(hexylsilanes). A simlar reaction at 70 °C resulted in selective cyclopolymerization of hexylsilane to yield a cyclic polymer with an average molecular weight of Mn = 1450 (Mw/Mn = 1.01, GPC polystyrene standard). The 1H NMR, 29Si­{1H} DEPT NMR, and IR spectroscopic data indicated the presence or absence of the −SiH2R end groups of the polymer and its acyclic or cyclic structure. Addition of hexylsilane to the solution of the poly­(hexylsilanes) containing the acyclic polymer (Mn = 1330) and heating the mixture in the presence of 5 mol % of [Ni­(dmpe)2] catalyst formed a polymer composed of the cyclic molecules without a change in the average molecular weight. The polymerization of phenylsilane catalyzed by [Ni­(dmpe)2] also yielded the cyclic poly­(phenylsilane). The reaction using a mixture of [Ni­(cod)2] (cod = 1,5-cyclooctadiene) and PMe3 as the catalyst produced acyclic and/or cyclic poly­(phenylsilanes) depending on the conditions. 9,9-Dihydrosilafluorene reacted with [PdMe2(dmpe)] to afford a persilylated palladacyclopentane, [Pd­(SiC12H8)4(dmpe)], with four 1,1-silafluorene units.