Arene C-H Bond Coordination versus C-H Bond Cleavage in Low-Valent Group 6 Carbonyl Pincer Complexes

Sara R.M.M. De Aguiar, Berthold Stöger, Ernst Pittenauer, Günter Allmaier, Luis F. Veiros, Karl Kirchner

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The reaction of hexacarbonyl group 6 complexes with the P(CH)P ligand N,N′-bis(diisopropylphosphino)-N,N′-dimethyl-1,3-diaminobenzene was investigated. The objective was to obtain PCP pincer complexes via directed C-H bond activation and cleavage. In the case of chromium and molybdenum, complexes [Cr(κ3P,CH,P-P(CH)PNMe-iPr)(CO)3] and [Mo(κ3P,CH,P-P(CH)PNMe-iPr)(CO)3], featuring η2-Caryl-H bonds, were formed and no C-H bond cleavage took place. With tungsten the expected seven-coordinate hydrido carbonyl W(II) complex [W(κ3P,C,P-PCPNMe-iPr)(CO)3H] was formed. DFT mechanistic studies corroborate the experimental observations and indicate that the M-H bond strength grows in the order Cr-H < Mo-H < W-H, explaining the preference for the hydride complex only in the case of W. X-ray structures of these complexes are presented.

Original languageEnglish
Pages (from-to)3032-3039
Number of pages8
JournalOrganometallics
Volume35
Issue number17
DOIs
Publication statusPublished - 12 Sep 2016

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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