N₂ Functionalization via Molybdenum‐Nitride Complex: Stepwise BH Bond Additions

Abstract

Reactivity of (triphosphine)MoIV‐nitrido complex generated by N2 splitting, toward boranes is reported. The simple adduct Mo≡N→BH3 is observed with BH3.SMe2 while 1,2 addition is evidenced with 9‐BBN leading to H‐Mo=NBR2. A second addition of BH3.SMe2 is facile and forms an unprecedented complex featuring two bridging H between two B and the Mo centers. Addition of PMe3 or BH3.SMe2 promotes reductive elimination and N‐H bond formation. The full sequence of functionalization at Mo≡N obtained after N2 splitting is therefore evidenced in this work.