The reaction of [Cp2 ttZr(μ3-S) 2{Ir(CO)2}2] (Cptt = η5-1,3-di-tert-butylcyclopentadienyl) with dppe (1,2-bis-(diphenylphosphino)ethane) affords the ion-pair compound [Ir(CO)(dPPe)2][Cp2 ttZr(μ-S) 2Ir(CO)2] (2). The related compound [Rh(dPPe) 2][Cp2 ttZr(μ-S)2Rh(CO) 2] (5) has been obtained in solution under a carbon monoxide atmosphere by reaction of [Cp2 ttZr(μ3-S) 2{Rh(CO)2}2] with dppe through the intermediate heterotrinuclear compound [Cp2 ttZr(μ3-S) 2{Rh(dppe)}{Rh(CO)2}] (4). Reaction of the heterodinuclear anion [Cp2 ttZr(μ-S)2Ir(CO) 2]-, generated in situ, with [Rh(μ-Cl)(cod)] 2, [RhCl2(CO)2]- and [Pd(μ-Cl)-(η3-C3H5)]2 affords the d0-d8-d8 early-late compounds [Cp 2 ttZr(μ3-S)2{Ir(CO) 2}{Rh(cod)}] (6), [Cp2 tt-Zr(μ3-S) 2{Ir(CO)2}{Rh(CO)2}] (7), and [Cp 2 ttZr(μ3-S)2{Ir(CO) 2}{Pd(η3-C3H5)}] (8) each with a symmetrical trigonal-bipyramidal M3(μ3-S)2 heterotrimetallic metal-sulfur core. In the same way, the reaction of [Cp 2 ttZr(μ-S)2M(CO)2]- (M = Rh, Ir) with [AuCl(PPh3)] leads to the preparation of the d 0-d8-d10 early-late compounds [Cp 2 ttZr(μ-S)2(Ir(CO)2}{Au(PPh 3)}] (9) and [Cp2 ttZr(μ-S) 2{Rh(CO)2}{Au(PPh3)}] (10) with an open M 3(μ3-S)(μ2-S) heterotrimetallic metal-sulfur framework. On the other hand, treatment of the bis(hydrosulfido) zirconium compound [Cp2 ttZr(SH)2] with triethylamine followed by addition of [Pd(μ-Cl)(η3-C 3H5)]2 or [AuCl(PPh3)] affords the sulfido-bridged early-late heterobimetallic compounds [Cp2 ttZr(μ3-S)2{Pd(η3-C 3H5)}2] (11) and [Cp2 ttZr(μ-S)2(Au(PPh3)}2] (12). The molecular structure of complexes 9 and 12 determined by X-ray diffraction methods are also described.

The financial support from Ministerio de Educación y Ciencia (MEC/FEDER) is gratefully acknowledged (Projects CTQ2006-03973/BQU and Factoría de Cristalización, CONSOLIDER INGENIO-2010).

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