OSMIUM(VI) COMPLEXES OF TETRATHIOTUNGSTATE

The anionic organoosmium complexes [Y][Os(N)R(2)Cl(2)] (Y = PPh(4), NB u(4); R = CH3, CH(2)SiMe(3)) reacted with. (NH4)(2)WS4 or (NH4)(2)MoS4 to give the heterobimetallic complexes [Y] [Os(N)R(2)(mu-S)(2)MS(2)] (M = W, Mo). The reaction of [Os(N) (CH(2)SiMe(3))(2)Cl](2) with an ex cess of (NH4)(2)WS4 in CH2Cl2 at room temperature produced a trimetall ic complex in which two organonitridoosmium units are bridged by a tet rathiotungstate group, (2)(N)Os(mu-s)(2)W(mu-S)(2)OS(N)(CH(2)SiMe(3))( 2). The molecular structures of [NBu(4)][Os(N)(CH(2)SiMe(3))(2)(mu-S)( 2)WS2] and [(Me(3)SiCH(2))(2)(N)Os](2)(mu-WS4) were determined by X-ra y diffraction. Crystals of [NBu(4)][Os(N)(CH2-SiMe(3))(2)(mu-S)(2)WS2] are monoclinic in space group C2/c with a = 39.358(9) Angstrom, b = 1 1.074(3) Angstrom, c = 18.685(9) Angstrom, beta = 109.37(3)degrees,Z = 8, R = 0040, and R(W) = 0.048. Crystals of [(Me(3)SiCH(2))(2)(N)Os](2 )(mu-WS4) are triclinic in space group <P(1)over bar> with a = 10.012( 3) Angstrom, b = 11.979(5) Angstrom, c = 15.775(4) Angstrom, a = 105.5 1(3)degrees, beta = 97.34(2)degrees, gamma = 112.03(3)degrees, Z = 2, R = 0.026, and R(W) = 0.030. The reaction between [(Me(3)SiCH(2))(2)(N )Os](2)(mu-WS4) and Ph(4)PCl gave [PPh(4)](2)[R(2)Os(N)Cl](2)(mu-WS4).