REACTIONS OF [W(NH=NR)(CO)(2)(PPH(3))(2)(-] WITH AZIDE AND AMINES THAT OCCUR WITHOUT DISPLACEMENT OF THE NH-NR LIGAND()][PF6)

The d(6) tungsten phenyldiazene complex [trans,trans-W(NH=NPh)(CO)(2)( NO) (PPh(3))(2)(+)][PF6-] (1a) reacted with ammonia, methylamine or hy drazine at -78 degrees C giving ans-W(NH=NPh)(CO)(NO)(NH(2)R)(PPh(3))( 2)(+)][PF6-] (2a, R = H; 2b, R = CH3; 2c, R = NH2) as purple salts in good yield, along with one equivalent of carbon monoxide. Sodium azide reacted with 1a or the p-tolyldiazene derivative [trans,trans-W(NH=NT ol) (CO)(2)(NO)(PPh(3))(2)(+)][PF6-] (1b) in the presence of a proton source giving CO and [trans,trans-W(NHNHR)(N-3)(2)(NO)(PPh(3))(2)] (3b , R = Tol), neutral bis(azido) complexes containing arylhydrazido liga nds. These reactions involving nitrogen nuclphiles are in striking con trast with known activity of 1a,b with Br- that gives [trans-W(Br)(CO) (2)(NO)(PPh(3))(2)] amd free NH = NPh. Copyright (C) 1996 Elsevier Sci ence Ltd