A Low-Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

Toward nitrogen functionalization, reactive terminal transition metal nitrides with high d‐electron counts are of interest. A series of terminal Mo^(IV) nitride complexes were prepared within the context of exploring nitride/carbonyl coupling to cyanate. Reduction affords the first Mo^(II) nitrido complex, an early metal nitride with four valence d‐electrons. The binding mode of the para‐terphenyl diphosphine ancillary ligand changes to stabilize an electronic configuration with a high electron count and a formal M−N bond order of three. Even with an intact Mo≡N bond, this low‐valent nitrido complex proves to be highly reactive, readily undergoing N‐atom transfer upon addition of CO, releasing cyanate anion.