The Rh-III complex [(PNP)Rh(CN)(CH3)][1] 5, obtained by oxidative addition of methyl iodide to [(PNP)Rh(CN)] 2, reacts selectively in two pathways: In aprotic solvents C-1 reductive elimination of methyl iodide followed by its electrophilic attack on the cyano ligand takes place, giving the methyl isonitrile Rh-1 complex [(PNP)Rh(CNCH3)][1] 3, while in protic solvents C-C reductive elimination of acetonitrile takes place forming an iodo Rh-1 complex [(PNP)Rhl]) 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.