New early zirconium-sulfido metallaligands for late transition metals; Synthesis and reactivity of [(Cp2Zr)-Zr-tt(SH)(2)] and [(Cp2Zr)-Zr-tt(SH)(OTf)]

The bishydrosulfido zirconium metallocene compound [(Cp2Zr)-Zr-tt(SH)(2)] ( 2) containing the bulky eta(5)-1,3-di-tert-butylcyclopentadienyl (Cp-tt) li gand is readily accessible from [(Cp2Zr)-Zr-tt(CH3)(2)] (1) upon treatment with H2S. Reaction of 2 with methyltriflate gives the monohydrosulfido comp lex [(Cp2Zr)-Zr-tt(SH) (OSO2CF3)] (3) which exists as two isomers in soluti on, and has been characterized by X-ray diffraction methods. Complex 2 is e ffective metallaligand for the controlled synthesis of new trinuclear early -late heterobimetallic complexes (ELHB) with a ZrRh2 core such as [(Cp2Zr)- Zr-tt(mu(3)-S)(2){Rh(CO)(2)}(2)] (4).