Chemistry of coordinatively unsaturated organoruthenium amidinates as entry to homogeneous catalysis

Hideo Nagashima, Hideo Kondo, Taizo Hayashida, Yoshitaka Yamaguchi, Mitsuru Gondo, Satoshi Masuda, Kazuma Miyazaki, Kouki Matsubara, Karl Kirchner

Research output: Contribution to journalArticlepeer-review

100 Citations (Scopus)

Abstract

The chemistry of coordinatively unsaturated organoruthenium complexes is reviewed in this article. In particular, the subject is focused on neutral and cationic organoruthenium amidinates, which formally have 16 valence electrons and show signs of coordinative unsaturation. The ruthenium amidinates, (η5-C5Me5)Ru(η-amidinate) (1), and their isoelectronic analogues, [η6-arene)Ru(η -amidinate)]+ (2), are synthesized and characterized; a possible stabilizing factor of the unsaturated metal center is weak coordination of π-electrons in the amidinates ligands. Reactions of various two-electron donor ligands with 1 or 2 reveal the strong w-donor property of 1 and Lewis acid nature of 2. One or two-electron redox processes of 1 in the reactions with organic halides are studied by isolation of the corresponding Ru(III) and Ru(IV) products; the results lead to their catalysis for the Tsuji-Trost reaction and the intramolecular Kharasch reaction. The treatment of 2 with trimethylsilyldiazomethane results in the formation of cationic amidinato-carbene complexes, which involve unusual reversible metal-to-carbon silyl group migration.

Original languageEnglish
Pages (from-to)177-190
Number of pages14
JournalCoordination Chemistry Reviews
Volume245
Issue number1-2
DOIs
Publication statusPublished - Oct 2003

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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