Synthesis of [Ru(CO)2(PPh3)(SP)] and [Ru(CO)(PPh3)2(SP)] and their catalytic activities for the hydroamination of phenylacetylene

Eiichiro Mizushima, Naoto Chatani, Fumitoshi Kakiuchi

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The reaction of [Ru(CO)2(PPh3)3] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)2(PPh3)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC6H4NN)(CO)2(PPh3) 2]BF4 (4) with NaBH4 and 2 in 50% yield. When "Ru(CO)(PPh3)3" generated by the reaction of [RuH2(CO)(PPh3)3] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh3)2(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH4PF6 or H3PW12O40 proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H3PW12O40 as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction.

Original languageEnglish
Pages (from-to)5739-5745
Number of pages7
JournalJournal of Organometallic Chemistry
Volume691
Issue number26
DOIs
Publication statusPublished - 2006 Dec 15

Keywords

  • Anilines
  • Hydroamination
  • Phenylacetylene
  • Zero-valent ruthenium complexes
  • o-Styrylphosphine

ASJC Scopus subject areas

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

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