Competitive C-I versus C-CN reductive elimination from a RhIII complex. Selectivity is controlled by the solvent

Moran Feller; Mark A. Iron; Linda J.W. Shimon; Yael Diskin-Posner; Gregory Leitus; David Milstein

doi:10.1021/ja8046798

Competitive C-I versus C-CN reductive elimination from a Rh^III complex. Selectivity is controlled by the solvent

Moran Feller, Mark A. Iron, Linda J.W. Shimon, Yael Diskin-Posner, Gregory Leitus, David Milstein

Weizmann Institute of Science, Israel

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

32 Citations (Scopus)

Abstract

The Rh^III complex [(PNP)Rh(CN)(CH₃)][I] 5, obtained by oxidative addition of methyl iodide to [(PNP)Rh(CN)] 2, reacts selectively in two pathways: In aprotic solvents C-I reductive elimination of methyl iodide followed by its electrophilic attack on the cyano ligand takes place, giving the methyl isonitrile RhI complex [(PNP)Rh(CNCH₃)][I] 3, while in protic solvents C-C reductive elimination of acetonitrile takes place forming an iodo RhI complex [(PNP)RhI] 9. Reaction of 2 with ethyl iodide in aprotic solvents gave the corresponding isonitrile complex, while in protic solvents no reactivity was observed. The selectivity of this reaction is likely due to a hydrogen bond between the cyano ligand and the protic solvent, as observed by X-ray diffraction, which retards electrophilic attack on this ligand.

Original language	English
Pages (from-to)	14374-14375
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	130
Issue number	44
DOIs	https://doi.org/10.1021/ja8046798
Publication status	Published - Nov 5 2008

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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Competitive C-I versus C-CN reductive elimination from a Rh^III complex. Selectivity is controlled by the solvent. / Feller, Moran; Iron, Mark A.; Shimon, Linda J.W.; Diskin-Posner, Yael; Leitus, Gregory; Milstein, David.

In: Journal of the American Chemical Society, Vol. 130, No. 44, 05.11.2008, p. 14374-14375.

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

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abstract = "The RhIII complex [(PNP)Rh(CN)(CH3)][I] 5, obtained by oxidative addition of methyl iodide to [(PNP)Rh(CN)] 2, reacts selectively in two pathways: In aprotic solvents C-I reductive elimination of methyl iodide followed by its electrophilic attack on the cyano ligand takes place, giving the methyl isonitrile RhI complex [(PNP)Rh(CNCH3)][I] 3, while in protic solvents C-C reductive elimination of acetonitrile takes place forming an iodo RhI complex [(PNP)RhI] 9. Reaction of 2 with ethyl iodide in aprotic solvents gave the corresponding isonitrile complex, while in protic solvents no reactivity was observed. The selectivity of this reaction is likely due to a hydrogen bond between the cyano ligand and the protic solvent, as observed by X-ray diffraction, which retards electrophilic attack on this ligand.",

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AU - Feller, Moran

AU - Iron, Mark A.

AU - Shimon, Linda J.W.

AU - Diskin-Posner, Yael

AU - Leitus, Gregory

AU - Milstein, David

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N2 - The RhIII complex [(PNP)Rh(CN)(CH3)][I] 5, obtained by oxidative addition of methyl iodide to [(PNP)Rh(CN)] 2, reacts selectively in two pathways: In aprotic solvents C-I reductive elimination of methyl iodide followed by its electrophilic attack on the cyano ligand takes place, giving the methyl isonitrile RhI complex [(PNP)Rh(CNCH3)][I] 3, while in protic solvents C-C reductive elimination of acetonitrile takes place forming an iodo RhI complex [(PNP)RhI] 9. Reaction of 2 with ethyl iodide in aprotic solvents gave the corresponding isonitrile complex, while in protic solvents no reactivity was observed. The selectivity of this reaction is likely due to a hydrogen bond between the cyano ligand and the protic solvent, as observed by X-ray diffraction, which retards electrophilic attack on this ligand.

AB - The RhIII complex [(PNP)Rh(CN)(CH3)][I] 5, obtained by oxidative addition of methyl iodide to [(PNP)Rh(CN)] 2, reacts selectively in two pathways: In aprotic solvents C-I reductive elimination of methyl iodide followed by its electrophilic attack on the cyano ligand takes place, giving the methyl isonitrile RhI complex [(PNP)Rh(CNCH3)][I] 3, while in protic solvents C-C reductive elimination of acetonitrile takes place forming an iodo RhI complex [(PNP)RhI] 9. Reaction of 2 with ethyl iodide in aprotic solvents gave the corresponding isonitrile complex, while in protic solvents no reactivity was observed. The selectivity of this reaction is likely due to a hydrogen bond between the cyano ligand and the protic solvent, as observed by X-ray diffraction, which retards electrophilic attack on this ligand.

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