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

doi:10.1002/chem.200801171

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

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article › peer-review

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 Rh^I 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 language	English
Pages (from-to)	8183-8194
Number of pages	12
Journal	Chemistry - A European Journal
Volume	14
Issue number	27
DOIs	https://doi.org/10.1002/chem.200801171
Publication status	Published - Sep 19 2008

Keywords

Anagostic interaction
C-H activation
Carbonyl ligands
Phosphines
Rhodium

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.200801171

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Montag, M., Efremenko, I., Cohen, R., Leitus, G., Shimon, L. J. W., Diskin-Posner, Y., Ben-David, Y., Martin, J. M. L., & Milstein, D. (2008). 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. Chemistry - A European Journal, 14(27), 8183-8194. https://doi.org/10.1002/chem.200801171

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 journal › Article › peer-review

Montag, M, Efremenko, I, Cohen, R, Leitus, G, Shimon, LJW, Diskin-Posner, Y, Ben-David, Y, Martin, JML & Milstein, D 2008, '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', Chemistry - A European Journal, vol. 14, no. 27, pp. 8183-8194. https://doi.org/10.1002/chem.200801171

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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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.",

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