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Issue 15, 2016
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Hydrodealkoxylation reactions of silyl ligands at platinum: reactivity of SiH3 and SiH2Me complexes

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Abstract

The platinum(II) complex [Pt(H)2(dcpe)] (1; dcpe = 1,2-bis(dicyclohexylphosphino)ethane) reacts with an excess of the dialkoxymethylsilanes (HSiMe(OR)2; R = Me, Et) to give the bis(silyl) complex [Pt(SiH2Me)2(dcpe)] (3) and trialkoxymethylsilanes by hydrodealkoxylation reactions. These rearrangements of the silyl ligands involve Si–O bond activations. The exchange of the alkoxy moieties against silicon-bound hydrogen atoms occurs stepwise. The intermediate complexes [Pt(H){SiMe(OEt)2}(dcpe)] (5), [Pt{SiMe(OEt)2}2(dcpe)] (6), [Pt{SiHMe(OEt)}2(dcpe)] (7) and [Pt{SiHMe(OMe)}2(dcpe)] (8) were detected. Treatment of the complex 1 with an excess of dichloromethylsilane yields the bis(silyl) complex [Pt(SiMeCl2)2(dcpe)] (9). The hydrido silyl complex [Pt(H)(SiMeCl2)(dcpe)] (10) was identified as an intermediate. The reactions of the complexes [Pt(SiH3)2(dcpe)] (2) and [Pt(SiH2Me)2(dcpe)] (3) with iodomethane lead to a transfer of the SiH3 and SiH2Me ligands. Methylsilane and dimethylsilane, respectively, as well as the platinum diiodo complex [Pt(I)2(dcpe)] (11) were identified as main products.

Graphical abstract: Hydrodealkoxylation reactions of silyl ligands at platinum: reactivity of SiH3 and SiH2Me complexes

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Publication details

The article was received on 17 Dec 2015, accepted on 22 Feb 2016 and first published on 07 Mar 2016


Article type: Paper
DOI: 10.1039/C5DT04923G
Citation: Dalton Trans., 2016,45, 6394-6404
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    Hydrodealkoxylation reactions of silyl ligands at platinum: reactivity of SiH3 and SiH2Me complexes

    C. Mitzenheim, T. Braun, R. Laubenstein, B. Braun and R. Herrmann, Dalton Trans., 2016, 45, 6394
    DOI: 10.1039/C5DT04923G

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