The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)2(phosphine)2]+

An experimental and theoretical examination

Michael Montag, Irena Efremenko, Revital Cohen, Gregory Leitus, Linda J W Shimon, Yael Diskin-Posner, Yehoshoa Ben-David, Jan M L Martin, David Milstein

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The crystal structure of the new cation ic Rh1 complex trans-[Rh(CO)2(L)2]BF4 (L = a 2-(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OC-Rh-CO fragment and weak intramolecular C-H⋯Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OC-Rh-CO fragment. This linkage has also been demonstrated by comparison with a highly similar RhI complex, in which these C-H⋯Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.

Original languageEnglish
Pages (from-to)8183-8194
Number of pages12
JournalChemistry - A European Journal
Volume14
Issue number27
DOIs
Publication statusPublished - Sep 19 2008

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phosphine
Carbon Monoxide
Density functional theory
Crystal structure
Positive ions
Metals
Cations

Keywords

  • Anagostic interaction
  • C-H activation
  • Carbonyl ligands
  • Phosphines
  • Rhodium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)2(phosphine)2]+ : An experimental and theoretical examination. / Montag, Michael; Efremenko, Irena; Cohen, Revital; Leitus, Gregory; Shimon, Linda J W; Diskin-Posner, Yael; Ben-David, Yehoshoa; Martin, Jan M L; Milstein, David.

In: Chemistry - A European Journal, Vol. 14, No. 27, 19.09.2008, p. 8183-8194.

Research output: Contribution to journalArticle

Montag, Michael ; Efremenko, Irena ; Cohen, Revital ; Leitus, Gregory ; Shimon, Linda J W ; Diskin-Posner, Yael ; Ben-David, Yehoshoa ; Martin, Jan M L ; Milstein, David. / The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)2(phosphine)2]+ : An experimental and theoretical examination. In: Chemistry - A European Journal. 2008 ; Vol. 14, No. 27. pp. 8183-8194.
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