Reactions of transition-metal nitrido compounds with B(C6F5)3∶ crystal structure of [Re{NB(C6F5)3}(PMe2Ph)(S2CNMe2)2]

Abstract

The transition-metal nitrido complexes [Re(N)(PR₃)(S₂CNR′₂)₂] (PR₃ = PMe₂Ph, R′ = Me; PR₃ = PMePh₂, R′ = Et 1), [Re(N)(Cl)(PMePh₂)₂(S₂CNMe₂)] 2, [Mo(N)(S₂CNR₂)₃] (R = Me or Et) and [NBuⁿ₄][Os(N)(1,2-S₂C₆H₄)₂] reacted with the strong Lewis acid B(C₆F₅)₃ to yield the adducts [Re{NB(C₆F₅)₃}(PR₃)(S₂CNR′₂)₂] (PR₃ = PMe₂Ph, R′ = Me 3*; PR₃ = PMePh₂, R′ = Et 4), [Re{NB(C₆F₅)₃}(Cl)(PMePh₂)₂(S₂CNMe₂)] 5, [Mo{NB(C₆F₅)₃}(S₂CNR₂)₃] (R = Me 6 or 7) and [NBuⁿ₄][Os{NB(C₆F₅)₃}(1,2-S₂C₆H₄)₂] 8 (* indicates that the compound has been structurally characterised). Reactions of 3, 6 and 8 with competing strong Lewis bases have revealed differences in the stability of the MN–B interaction depending on the steric crowding around the metal centre. Reaction of 8 with MeO₃SCF₃ causes the formation of [Os{NB(C₆F₅)₃}{1,2-(S)(SMe)C₆H₄}(1,2-S₂C₆H₄)] 9.