Activation of Homolytic Si-Zn and Si-Hg Bond Cleavage, Mediated by a Pt-0 Complex, via Novel Pt-Zn and Pt-Hg Compounds

Yosi Kratish, Gregory Molev, Arseni Kostenko, Dennis Sheberla, Boris Tumanskii, Mark Botoshansky, Shigeru Shimada, Dmitry Bravo-Zhivotovskii, Yitzhak Apeloig

Research output: Contribution to journalArticlepeer-review

Abstract

The thermally stable [(tBuMe2Si)2M] (M=Zn, Hg) generate R3Si. radicals in the presence of [(dmpe)Pt(PEt3)2] at 60-80 C. The reaction proceeds via hexacoordinate Pt complexes, (M=Zn (2 a and 2 b), M=Hg (3 a and 3 b)) which were isolated and characterized. Mild warming or photolysis of 2 or 3 lead to homolytic dissociation of the Pt-MSiR3 bond generating silyl radicals and novel unstable pentacoordinate platinum paramagnetic complexes (M=Zn (5), Hg (6)) whose structures were determined by EPR spectroscopy and DFT calculations. SiM City: The thermally stable [(tBuMe2Si)2M] (M=Zn, Hg) generate R3Si. radicals in the presence of [(dmpe)Pt(PEt3)2]. The enhancing effect of the Pt complex on the homolytic cleavage of the Si-M bonds in [(tBuMe2Si)2M] is mediated by formation of octahedral hexacoordinate Pt-M trinuclear complexes.

Original languageEnglish
Pages (from-to)11817-11821
Number of pages5
JournalAngewandte Chemie - International Edition
Volume54
Issue number40
DOIs
StatePublished - 28 Sep 2015

Keywords

  • mercury
  • platinum
  • silyl radicals
  • trinuclear complexes
  • zinc

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Catalysis

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