Ligand-Dominated Activation of CO and CS by the Putative Nickel Phosphiniminato Intermediates.

Room-temperature photoactivation of the first- and second-generation PNP-pincer nickel azido complexes and in the presence of CO or CS afforded N-bound carbamates, dithiocarbamates, and isothiocyanates, providing insights into CO and CS activation and demonstrating how a seemingly small difference in the ligand structure significantly influences the reactivity. Theoretical calculations disclosed that the charge of the phosphorus atom plays a critical role in determining the nitrogen atom transfer to form a plausible nickel phosphiniminato intermediate.