TY - JOUR
T1 - Competitive C-I versus C-CN reductive elimination from a RhIII complex. Selectivity is controlled by the solvent
AU - Feller, Moran
AU - Iron, Mark A.
AU - Shimon, Linda J.W.
AU - Diskin-Posner, Yael
AU - Leitus, Gregory
AU - Milstein, David
PY - 2008/11/5
Y1 - 2008/11/5
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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U2 - 10.1021/ja8046798
DO - 10.1021/ja8046798
M3 - Article
C2 - 18847193
AN - SCOPUS:55549096043
VL - 130
SP - 14374
EP - 14375
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 44
ER -