Thermal reactions of alkyl(hydrido)(hydrosilyl)iridium(III) complexes: Generation of a hydrido(silylene)iridium(I) species via the reductive elimination of alkane and 1,2-H-shift from the silicon atom to the Ir(I) metal center

Masaaki Okazaki, Hiromi Tobita, Yasuro Kawano, Shinji Inomata, Hiroshi Ogino

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Heating of alkyl(hydrido)(hydrosilyl)iridium(III) complexes LnIr(R)(H) [Ln={η2-MesHSi(CH2)2PPh 2}(PMe3)2, Mes=2,4,6-C6H2Me3, R=Me, Et] led to the reductive elimination of alkane. Subsequently, the resulting hydrosilyliridium(I) intermediate LnIr (A) activated the intramolecular carbon-hydrogen bond to give Ir(H){η3-CH2C6H2(CH 3)2SiH(CH2)2PPh 2}(PMe3)2. In the presence of MeOH, A was quickly trapped with MeOH to give a methoxysilyliridium(III) complex Ir(H)22-Mes(MeO)Si(CH2) 2PPh2}(PMe3)2. This reactivity of A with MeOH clearly supports the occurrence of a 1,2-H-shift from the silyl silicon atom to the iridium center to generate a hydrido(silylene)iridium(I) species Ir(H)[η2-{=SiMes(CH2)2PPh 2}](PMe3)2.

Original languageEnglish
Pages (from-to)1-13
Number of pages13
JournalJournal of Organometallic Chemistry
Volume553
Issue number1-2
DOIs
Publication statusPublished - 1998 Feb 25

Keywords

  • 1,2-migration
  • Carbon-hydrogen bond activation
  • Silylene complex
  • Silyliridium

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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