REACTION OF CP-ASTERISK-MOCL4 AND CP-ASTERISK-WCL4 WITH H2O, H2S, AMINES, AND HYDRAZINES - FORMATION OF THE TRIOXO ANIONS [CP-ASTERISK-MO(O)3]- AND [CP-ASTERISK-W(O)3]- AND THE TRISULFIDO ANION [CP-ASTERISK-W(S)3]-

In the presence of aqueous NaOH and air, Cp*WCl4 undergoes hydrolysis and oxidation to form CP*W(O)2Cl. When air is excluded, two W(V) intermediates are detected in the above reaction for which spectroscopic evidence indicates the formulations Cp*WCl3(OH) and Cp*WCl2-(OH)2. In the absence of air, Cp*MoCl4 reacts with NaOH(aq) to cleanly yield the Mo(V) compound CP*Mo(O)Cl2, but in the presence of air oxidation occurs to give the Mo(VI) complex Cp*Mo(O)2Cl. Both Cp*WCl4 and Cp*MoCl4 react with aqueous ButNH2 in the presence of air to form the trioxo anions [CP*M(O)3]-, which have been isolated as their [ButNH3]+ salts. The trioxo anions are also produced upon treatment Of CP*M(O)2Cl or [CP*M(O)2]2(mu-O) with aqueous ButNH2. [(Ph3P)2N]+ and[Bun4N]+ salts of [Cp*W(O)3]- were obtained by metathesis reactions, and the reaction of [ButNH3][CP*W(O)3] with EtC{O}CH=CH2 gave the salt [But(EtC{O}CH2CH2)NH2][CP*W(O)3]. The complex Cp*WCl4 was also observed to react with anhydrous ButNH2 in the absence of air to form Cp*W(NBut)Cl2, which in turn gave Cp*W-(O)(NBut)Cl upon exposure to moist air. With phenylhydrazine, Cp*WCl4 reacted in air to give the bis(hydrazinido) complex Cp*W(NNHPh)2Cl. With H2S in air, both Cp*WCl4 and Cp*MoCl4 reacted to give mixtures of the known dinuclear compounds [CP*M(S)]2(mu-S)2 and [Cp*M-(S)]2(mu-S2), but in the presence of NEt3, CP*WCl4 and H2S reacted to give the new trisulfido anion [CP*W(S)3]-. In exploratory reactions of [CP*W(O)3]- with unsaturated organic substrates, phenylketene was observed to react with this trioxo anion to give a new complex formed via net [2 + 2] cycloaddition of a W=O bond across the ketene C=C bond, and two molecules of MeO{O}CC=CC{O}OMe were taken up by [CP*W(O)3]- to form a new complex with a six-membered WOC(R)=C(R)C(R)=C(R) ring. Crystal structures are reported for [But(EtC{O}CH2CH2)NH2][Cp*W(O)3], [ButNH3][Cp*NH3][Cp*W(O)3].1/2[ButHN3]Cl, [Ph3P)2N][Cp*W(O)3].2H2O, [Et3NH][Cp*W(S)3], and [Cp*W(S)2(mu-S)2.