Photolysis of Alkoxy-Substituted Disilanyliron Complexes: Preparation of Donor-Stabilized Bis(silylene)iron Complexes and the Crystal Structure of (Me2Si)⩵[(η5-C5Me5)Fe(CO)]⩵[SiMe(OMe)]⩵OMe

Hiromi Tobita, Keiji Ueno, Mamoru Shimoi, Hiroshi Ogino

Research output: Contribution to journalArticlepeer-review

117 Citations (Scopus)

Abstract

Photolysis of Cp'Fe(CO)2SiMe2SiMe(OMe)2(2b) (Cp' = η5-C5Me5) afforded the novel donor-stabilized bis(silylene)iron complexes (Me2Si)⩵[Cp'Fe(CO)]⩵[SiMe(OMe)]--OMe, 3b and 3b', as a pair of geometrical isomers in ca. 2:1 ratio. The X-ray crystal structure of 3b shows very short Fe-Si bonds (2.21 and 2.22 Å), fairly long Si-O(trivalent) bonds (1.79 and 1.80 Å), and an almost planar configuration of the iron atom and terminal methoxy or methyl groups at each silicon. The sp2character of the silicon atoms is further supported by the remarkable low-field chemical shifts of the 29Si NMR signals of 3b and 3b' (δ 127.4, 121.1, 98.9, and 93.9 ppm). These structural and spectroscopic data indicate that the Fe-Si bonds take on partial double-bond character [“bis(silylene)iron” structure], while the Si-O(trivalent) bonds contain covalent and dative contributions. Photolysis of several other alkoxy-substituted disilanyliron complexes also afforded bis(silylene)iron complexes.

Original languageEnglish
Pages (from-to)3415-3420
Number of pages6
JournalJournal of the American Chemical Society
Volume112
Issue number9
DOIs
Publication statusPublished - 1990 Jan

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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