N 2 Functionalization via Molybdenum-Nitride Complex: Stepwise BH Bond Additions.

Reactivity of (triphosphine)Mo IV -nitrido complex generated by N 2 splitting, toward boranes is reported. The simple adduct Mo≡N→BH 3 is observed with BH 3 .SMe 2 while 1,2 addition is evidenced with 9-BBN leading to H-Mo=NBR 2 . A second addition of BH 3 .SMe 2 is facile and forms an unprecedented complex featuring two bridging H between two B and the Mo centers. Addition of PMe 3 or BH 3 .SMe 2 promotes reductive elimination and N-H bond formation. The full sequence of functionalization at Mo≡N obtained after N 2 splitting is therefore evidenced in this work.