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Issue 23, 2014
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Direct hydrosilylation by a zirconacycle with β-hydrogen

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Azasilazirconacycle Cp2Zr{κ2-N(SiHMe2)SiHMeCH2} (1) and formaldehyde react through an uncatalyzed addition reaction (hydrosilylation) to form an exocyclic methoxysilyl-substituted zirconacycle. Although 1 contains 2-center-2-electron SiH groups, this transformation parallels the reactions of non-classical [Cp2ZrN(SiHMe2)2]+ ([2]+) with carbonyls. Reactions of 1 with a series of nucleophilic and electrophilic agents were explored, as well as reactions of related β-SiH-containing silazidozirconium compounds, to develop a rationale for the unexpected hydrosilylation. For example, carbon monoxide and 1 react at the Zr–C bond to form Cp2Zr{κ2-OC([double bond, length as m-dash]CH2)SiHMeN(SiHMe2)} (7). The Lewis acid B(C6F5)3 also reacts at the Zr–C bond to give Cp2Zr{N(SiHMe2)SiHMeCH2B(C6F5)3} (8). OPEt3 and N,N-dimethylaminopyridine (DMAP) do not appear to interact with 1. In contrast, OPEt3 and DMAP react with non-classical compounds [2]+ and zwitterionic 8.

Graphical abstract: Direct hydrosilylation by a zirconacycle with β-hydrogen

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The article was received on 05 Mar 2014, accepted on 10 Apr 2014 and first published on 24 Apr 2014

Article type: Paper
DOI: 10.1039/C4DT00658E
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2014,43, 8644-8653
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    Direct hydrosilylation by a zirconacycle with β-hydrogen

    K. Yan, A. Pindwal, A. Ellern and A. D. Sadow, Dalton Trans., 2014, 43, 8644
    DOI: 10.1039/C4DT00658E

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