Reactivity of molybdenum–nitride complex bearing pyridine-based PNP-type pincer ligand toward carbon-centered electrophiles

Abstract

A molybdenum–nitride complex bearing a pyridine-based PNP-type pincer ligand derived from dinitrogen is reacted with various kinds of carbon-centered electrophiles to functionalize the nitride ligand in the molybdenum complex. Methylation with MeOTf and acylation with diphenylacetyl chloride of the nitride complex afford the corresponding imide complexes via a carbon–nitrogen bond formation. In the case of reactions with phenylisocyanate and diphenylketene, the PNP ligand works as a non-innocent ligand to form the corresponding ureate and acylimide complexes, respectively. These newly synthesized complexes are characterized by X-ray analysis. As a further transformation of the prepared imide complexes, hydrolysis of the molybdenum–acylimide complex proceeds to give the corresponding amide as an organonitrogen compound together with the corresponding molybdenum–oxo complex. This result indicates that the nitrogen molecule is converted into organic amide mediated by the molybdenum–nitride complex.