Preparation of sulfide-bridged di- or trinuclear pyrrolylimido and diazoalkane complexes derived from a tungsten dinitrogen complex

Tungsten pyrrolylimido and diazoalkane complexes, cis,mer- [WCl2(NNC4H4)(PM e2Ph)(3)] and cis,mer- [WCl2(NN=CRR')(PMe2Ph)(3)], which are readily derive d from the dinitrogen complex cis- [W(N-2)(2)(PMe2Ph)(4)], reacted with [PP h4](2)[WS4] to give the sulfide-bridged di- or trinuclear pyrrolylimido and diazoalkane complexes, [PPh4][WCl(NNC4H4)(PMe2Ph)(2)(mu-S)(2)WS2] (4) and [PPh4][WCl(NN=CRR')(PMe2Ph)(2)(mu-S)(2)WS2] (R = R' = Me (5a); R = Me, R' = Ph; R = H, R' = p-MeC6H4), or [{WCl(NNC4H4)(PMe2Ph)(2)(mu-S)(2)}(2)W] (7) and [{WCl(NN=CMePh)(PMe2Ph)(2)(mu-S)(2)}(2)W]. Treatment of 4 or 5a with te traalkylthiuram disulfide resulted in the formation of sulfide-dithiocarbam ate complexes: [W(NNC4H4)(PMe2Ph)(S2CNR,)(mu-S)(2)WS(S2CNR2)] (R = Et, Pr-i (9b)) and [W(NN=CMe2)(PMe2Ph) (S2CNEt2)(mu-S)(2)WS(S2CNEt2)]. On the other hand, replacement of two PMe2Ph Iigands in 4 and 5 by Ph2PCH2CH2PPh2 (dppe ) afforded [PPh4][WCl(NNC4H4)(dppe)(mu-S)(2)WS2] and [PPh4][WCl(NN=CRR')(dp pe)(mu-S)(2)WS2] (R = R' = Me; R = Me, R' = Ph (12b)), where 12b has been s hown to react further with [RhCl(cod)](2) (cod = 1,5-cyclooctadiene) to giv e a bimetallic trinuclear complex [WCl(NN=CMePh)(dppe)(mu-S)(2)W(mu-S)(2)Rh (cod)] (13). Detailed structures have been determined by X-ray analyses for 4, 5a, 7, 9b, and 13.