Jump to main content
Jump to site search

Issue 35, 2011
Previous Article Next Article

Reaction of bis(o-phosphinophenyl)silane with M(PPh3)4 (M = Ni, Pd, Pt): synthesis and structural analysis of η2-(Si–H) metal(0) and pentacoordinate silyl metal(II) hydride complexes of the Ni triad bearing a PSiP-pincer ligand

Author affiliations

Abstract

Reactions of bis(o-(diphenylphosphino)phenyl)methylsilane with M(PPh3)4 (M = Ni, Pd, Pt) were investigated. When M = Ni or Pd, synthesis and isolation of η2-(Si-H) complexes of mononuclear Ni(0) and Pd(0) were achieved for the first time as frozen intermediates for oxidative addition of the Si–H bond. Structural analysis by X-ray and NMR spectroscopy disclosed that their η2-(Si–H) structures were maintained in both solid and solution states and coordination of the Si–H bond to the metal center was relatively weak. On the other hand, reaction with a platinum(0) complex afforded two kinds of pentacoordinate silyl platinum(II) hydride complexes having a PSiP-pincer ligand, which underwent unique thermal isomerization from a square-pyramidal cis-H–Pt–Si to a trigonal-bipyramidal trans-H–Pt–Si isomer. Mechanistic investigations revealed that this isomerization proceeded via an intramolecular rearrangement process probably through a turnstile rotation.

Graphical abstract: Reaction of bis(o-phosphinophenyl)silane with M(PPh3)4 (M = Ni, Pd, Pt): synthesis and structural analysis of η2-(Si–H) metal(0) and pentacoordinate silyl metal(ii) hydride complexes of the Ni triad bearing a PSiP-pincer ligand

Back to tab navigation

Supplementary files

Publication details

The article was received on 28 Mar 2011, accepted on 13 May 2011 and first published on 04 Jul 2011


Article type: Paper
DOI: 10.1039/C1DT10526D
Citation: Dalton Trans., 2011,40, 8814-8821
  •   Request permissions

    Reaction of bis(o-phosphinophenyl)silane with M(PPh3)4 (M = Ni, Pd, Pt): synthesis and structural analysis of η2-(Si–H) metal(0) and pentacoordinate silyl metal(II) hydride complexes of the Ni triad bearing a PSiP-pincer ligand

    J. Takaya and N. Iwasawa, Dalton Trans., 2011, 40, 8814
    DOI: 10.1039/C1DT10526D

Search articles by author

Spotlight

Advertisements