New Early Zirconium-Sulfido Metallaligands for Late Transition Metals; Synthesis and Reactivity of [Cptt2Zr(SH)2] and [Cptt2Zr(SH)(OTf)

Abstract

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).