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

The bishydrosulfido zirconium metallocene compound [Cptt2Zr(SH)2] (2) containing the bulky η5-1,3-di-tert-butylcyclopentadienyl (Cptt) ligand is readily accessible from [Cptt2Zr(CH3)2] (1) upon treatment with H2S. Reaction of 2 with methyltriflate gives the monohydrosulfido complex [Cptt2Zr(SH)(OSO2CF3)] (3) which exists as two isomers in solution, and has been characterized by X-ray diffraction methods. Complex 2 is an effective metallaligand for the controlled synthesis of new trinuclear early-late heterobimetallic complexes (ELHB) with a ZrRh2 core such as [Cptt2Zr(μ3-S)2{Rh(CO)2}2] (4).Financial support from Direccion General de Enseñanza Superior (DGES) (Projects PB9522212C1 and PB9421186) and a fellowship from the Ministerio de Educacion y Cultura (Dr. M. A. F. Hernandez-Gruel) are gratefully acknowledged.Peer reviewe