Making M–CN bonds from M–Cl in (PONOP)M and (dippe)Ni systems (M = Ni, Pd, and Pt) using t-BuNC

C–N bond activation of tert-butyl isocyanide in methanol using 2,6-bis(di-tert-butylphosphinito)pyridine (PONOP) metal (Ni, Pd, Pt) complexes and (dippe)NiCl2 are reported. t-BuOMe and t-BuCl were detected as organic products by GC–MS. Substitution of the metal-chloride by one molecule of tert-butyl isocyanide followed by carbonium ion loss/nucleophilic attack by chloride anion or methanol led to formation of a metal-cyanide bond.

The pincer PONOP complexes of Ni, Pd, and Pt have been found to react with tert-butyl isocyanide to give an adduct. This adduct is unstable, and loses tert-butyl carbonium ion to produce the cyanide product.Figure optionsDownload as PowerPoint slideHighlights
► We have observed C–N cleavage in nitriles.
► We have investigated reactions of Ni, Pd, and Pt pincer complexes.
► We report the synthesis of Ni, Pd, and Pt pincer cyanide complexes.