REACTIVITIES OF MOLYBDENUM AND TUNGSTEN DIAZOALKANE-ISOCYANIDE COMPLEXES DERIVED FROM DINITROGEN COMPLEXES

The diazoalkane-isocyanide complexes cis,trans-[MX2(NN=CMePh)(CNBut) ( PMe2Ph)(2)] (1a: M = Mo, X = Cl; 1b: M = W, X = Cl; 1c: M = W, X = Br) , readily derived from dinitrogen complexes cis-[M(N-2)(2)(PMe2Ph)(4)] , reacted with AlMe3 at room temperature to give the aminocarbene-diaz oalkane complexes cis,trans-[MX2(NN=CMePh) {=C(Me)-NHBut}(PMe2Ph)(2)] (2a: M = Mo, X = Cl; 2b: M = W, X = Cl; 2c: M = W, X = Br) after hydro lysis. Treatment of 1b with TfOH (Tf = CF3SO2) and then with (BuNC)-N- t at room temperature resulted in the formation of a cationic bis(isoc yanide)-diazoalkane complex trans,trans-[WCl(NN=CMePh)(CNBut)(2)(PMe2P h)(2)] [OTf] (3). The detailed structures of 2b and 3 have been determ ined by single-crystal X-ray analyses.