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 [NBu4n][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 [NBu4n][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 M equivalent to N-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.