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

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.