Synthesis and properties of intramolecularly base-stabilized (disilanyl-silylene)ruthenium and -iron complexes

Hiromi Tobita, Hitoe Kurita, Hiroshi Ogino

Research output: Contribution to journalArticlepeer-review

31 Citations (Scopus)

Abstract

Photolysis of the 3-methoxytrisilanyl complex CpM(CO)2SiMe2SiMe2SiMe2OMe (1a, M = Ru; 1b, M = Fe) afforded the intramolecularly methoxy-stabilized disilanyl-silylene complex Cp(OC)M{=SiMe2←O(Me)SiMe2SiMe2} (2a, M = Ru; 2b, M = Fe) as a primary product. Prolonged irradiation of the solution resulted in the decay of 2a,b with release of a dimethylsilylene moiety to give the methoxy-bridged bis(silylene) complex Cp(OC)M-{SiMe2⋯O(Me)⋯SiMe2} (3a, M = Ru; 3b, M = Fe). The X-ray crystal structure analysis of 2a revealed that 2a has a five-membered chelate ring and the Ru-Si(silylene) bond (2.291-(2) Å) is much shorter than the other Ru-Si bond (2.350(1) Å). It can be concluded from the bond lengths that the former possesses a partial double-bond character while the latter is a normal Ru-Si single bond. Photolysis of diisopropyl derivatives CpM(CO)2SiMe2SiiPr2SiMe 2OMe (4a, M = Ru; 4b, M = Fe) gave Cp(OC)M{=SiMe2←O(Me)SiMe2SiiPr 2} (5a, M = Ru; 5b, M = Fe) exclusively, in which the positions of substituents on silicon atoms in 5a and 5b were determined by 29Si-1H COLOC and NOESY NMR spectra. A mechanism involving 1,2-migration of the methoxydisilanyl group to the metal center was suggested. Irradiation of the tetrasilanyl complex CpFe(CO)2SiMe2SiMe2SiMe2SiMe 2OMe (6) caused a complicated reaction, giving at least five products having methoxy groups coordinated to silylene ligands.

Original languageEnglish
Pages (from-to)2850-2856
Number of pages7
JournalOrganometallics
Volume17
Issue number13
DOIs
Publication statusPublished - 1998 Jun 22

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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