Photoreactions of silyliron(II) complexes Cp{black star}Fe(CO)2SiMe3 (CP{black star} η5-C5H5, η5-C5Me5) in the presence of trihydrosilanes

Yasuro Kawano, Hiromi Tobita, Hiroshi Ogino

Research output: Contribution to journalArticlepeer-review

47 Citations (Scopus)

Abstract

The photochemistry of silyliron(II) complexes Cp{black star}Fe(CO)2SiMe3 (Cp{black star} η5-C5H5, η5-C5Me5) in the presence of trihydrosilanes is described. Three types of products were observed, depending on the bulkiness of the Cp{black star} ligands and the substituents on the trihydrosilanes: (η5-C5H5)Fe(CO)2SiMe3 reacts with tert-alkylsilanes RSiH3 (R tBu, C(Me2)2H) upon irradiation to give silylene-bridged diiron complexes (η5-C5H5)2Fe2(CO)3(μ-SiHR) in good yields. In contrast, (η5-C5Me5)Fe(CO)2SiMe3 reacts with the tert-alkylsilanes photochemically to give silyl monoiron complexes (η5-C5Me5)Fe(CO)2SiH2R exclusively. Using p-TolSiH3 instead of tert-alkylsilane, the main photolysis product was the hydridobis(silyl)iron complex Cp{black star}Fe(CO)SiMe3(H)SiH2-p-Tol. The X-ray crystal structure analysis of (η5-C5H5)2Fe2(CO)3(μ-SiHtBu) revealed that this complex adopts a geometry in which the two Cp rings and a SiH bond are located on the same side with respect to the SiFe2C four-membered ring. 29Si NMR spectra of the silylene-bridged diiron complexes showed signals at remarkably low field (δ 235.5-289.1 ppm). A mechanism for the formation of these silylene-bridged diiron complexes is proposed.

Original languageEnglish
Pages (from-to)125-143
Number of pages19
JournalJournal of Organometallic Chemistry
Volume428
Issue number1-2
DOIs
Publication statusPublished - 1992 Apr 28

ASJC Scopus subject areas

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

Fingerprint

Dive into the research topics of 'Photoreactions of silyliron(II) complexes Cp{black star}Fe(CO)<sub>2</sub>SiMe<sub>3</sub> (CP{black star} η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>, η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>) in the presence of trihydrosilanes'. Together they form a unique fingerprint.

Cite this