Maf. Hernandez-gruel et al., New early zirconium-sulfido metallaligands for late transition metals; Synthesis and reactivity of [(Cp2Zr)-Zr-tt(SH)(2)] and [(Cp2Zr)-Zr-tt(SH)(OTf)], EUR J INORG, (11), 1999, pp. 2047-2050
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).