Redistribution reactions of hydrosilanes mediated by the unsymmetrical and homometallic phosphido-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 ( μ-CO)(μ-PPh 2 )

Hisako Hashimoto, Hiromi Tobita, Hiroshi Ogino

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)

Abstract

Reactions of the unsymmetrical and homobimetallic phosphido-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-CO)(μ-PPh 2 ) (1) with various hydrosilanes gave rise to redistribution of the substituents on hydrosilanes. The reaction of 1 with 2 equiv. of secondary silane R 2 SiH 2 (R = Ph, p-Tol) caused effective aryl scrambling to afford a monoarylsilylene-bridged complex (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-SiRH)(μ-PPh 2 ) (2, R = Ph; 3, R = p-Tol) and a tertiary silane R 3 SiH (R = Ph, p-Tol). The signals of 29 Si and 31 P 1 H NMR spectra of these complexes appear at very low field ( 29 Si NMR; 2, δ 209.1, 1 J(SiH) = 185 Hz, 2 J(SiP) = 26 Hz; 3, δ 209.1 1 J(SiH) = 185 Hz, 2 J(SiP) = 27 Hz. 31 P NMR: 2, δ 224.5: 3, δ 225.0). Complex 2 and Ph 3 SiH were also formed by the reaction of 1 with 1 equiv. of dihydrodisilane HPh 2 SiSiPh 2 H. Similarly, the reaction of 1 with alkyldisilane HMe 2 SiSiMe 2 H proceeded smoothly to give the alkyl-scrambling product (η 5 -C 5 Me 5 )Fe 2 (CO) 4 (μ-SiMeH)(μ-PPh 2 ) (4) and Me 3 SiH. Some intermediates were observed in each reaction by NMR spectroscopy. A reaction mechanism containing silyl(silylene) intermediates is proposed.

Original languageEnglish
Pages (from-to)205-211
Number of pages7
JournalJournal of Organometallic Chemistry
Volume499
Issue number1-2
DOIs
Publication statusPublished - 1995 Sep 6

Keywords

  • Carbonyl
  • Cyclopentadienyl
  • Iron
  • Phosphorus
  • Silane
  • Silylene

ASJC Scopus subject areas

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

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