title: Hydrodealkoxylation reactions of silyl ligands at platinum: reactivity of SiH₃ and SiH₂Me complexes.
abstract: The platinum(ii) complex [Pt(H)2(dcpe)] (; 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)] () 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)] (), [Pt{SiMe(OEt)2}2(dcpe)] (), [Pt{SiHMe(OEt)}2(dcpe)] () and [Pt{SiHMe(OMe)}2(dcpe)] () were detected. Treatment of the complex with an excess of dichloromethylsilane yields the bis(silyl) complex [Pt(SiMeCl2)2(dcpe)] (). The hydrido silyl complex [Pt(H)(SiMeCl2)(dcpe)] () was identified as an intermediate. The reactions of the complexes [Pt(SiH3)2(dcpe)] () and [Pt(SiH2Me)2(dcpe)] () 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)] () were identified as main products.
authors.affiliation: Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, D-12489 Berlin, Germany. thomas.braun@chemie.hu-berlin.de.
authors.forename: Cathérine
authors.initials: C
authors.lastname: Mitzenheim
authors.affiliation: Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, D-12489 Berlin, Germany. thomas.braun@chemie.hu-berlin.de.
authors.forename: Thomas
authors.initials: T
authors.lastname: Braun
authors.affiliation: Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, D-12489 Berlin, Germany. thomas.braun@chemie.hu-berlin.de.
authors.forename: Reik
authors.initials: R
authors.lastname: Laubenstein
authors.affiliation: Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, D-12489 Berlin, Germany. thomas.braun@chemie.hu-berlin.de.
authors.forename: Beatrice
authors.initials: B
authors.lastname: Braun
authors.affiliation: Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, D-12489 Berlin, Germany. thomas.braun@chemie.hu-berlin.de.
authors.forename: Roy
authors.initials: R
authors.lastname: Herrmann