Reaction of Cp*MoCl4 and Cp*WCl4 with H2O, H2S, amines, and hydrazines. Formation of the trioxo anions [Cp*Mo(O)3]- and [Cp*W(O)3]- and the trisulfido anion [Cp*W(S)3]-

Both Cp*WCl[sub 4] and Cp*MoCL[sub 4] react with aqueous Bu[sup t]NH[sub 2] in the presence of air to form the trioxo anions [Cp*M(O)[sub 3]][sup [minus]], which have been isolated as their [Bu[sup t]NH[sub 3]][sup +] salts. The trioxo anions are also produced upon treatment of Cp*M(O)[sub 2]Cl or [Cp*M(O)[sub 2]][sub 2]([mu]-O) with aqueous Bu[sup t]NH[sub 2]. [Ph[sub 3]P[sub 2]N][sup +] and [Bu[sup n] [sub 4]N][sup +] salts of [Cp*W(O)[sub 3]][sup [minus]] were obtained by metathesis reactions, and the reaction of [Bu[sup t]NH[sub 3]][Cp*W(O)[sub 3]] with EtC[CO]CH=CH[sub 2] gave the salt [Bu[sup t](EtC[O]CH[sub 2]CH[sub 2])NH[sub 2]][Cp* W(O)[sub 3]]. The complex Cp*WCl[sub 4] was also observed to react with anhydrous Bu[sup t]NH[sub 2] in the absence of air to form Cp*W(NBu[sup t])Cl[sub 2], which in turn gave Cp*W(O)(NBu[sup t])Cl upon exposure to moist air. With phenylhydrazine, Cp*WCl[sub 4] reacted in air to give the bis(hydrazinido) complex Cp*W(NNHPh)[sub 2]Cl. With H[sub 2]S in air, both Cp*WCl[sub 4] and Cp*MoCl[sub 4] reacted to give mixtures of the known dinuclear compounds [Cp*M(S)][sub 2]([mu]-S)[sub 2] and [Cp*M(S)][sub 2]([mu]-S[sub 2]), but in the presence of NEt[sub 3], Cp*WCl[sub 4] and H[sub 2]S reacted to give the new trisulfido anion [Cp*W(S)[sub 3]][sup [minus]]. 40 refs., 5 figs., 12more » tabs.« less