SummaryReactions of the zirconium-sulfide metallocene anion [Cp tt 2 ZrS 2 ] 2-(Cp tt = η 5 -1,3-di-tertbutylcyclopentadienyl) with [{M(µ-Cl) with one molar-equiv of bis(diphenylphosphino)methane (dppm) gave the cisoid complexes [Cp tt 2 Zr(µ 3 -S) 2 {M(CO)} 2 (µ-dppm)] (M = Rh (9), Ir) with evolution of carbon monoxide.Monodentate phosphites, P(OMe) 3 and P(OPh) 3, react with 6 to give mixtures of the transoid and cisoid isomers [Cp tt 2 Zr(µ 3 -S) 2 {Rh(CO)(P(OR) 3 )} 2 ], which also exhibit a restricted rotation of the Cp tt rings. The molecular structures of complexes 6 and 9 have been determined by X-ray diffraction methods. Compound 6 in the presence of P-donor ligands, P(OMe) 3 , P(OPh) 3, and 40 PPh 3 , is a precursor of catalyst for the hydroformylation of oct-1-ene under mild conditions of pressure and temperature.

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).

Sulfido ligands meet the coordination and electronic requirements for stabilizing compounds containing divergent metal centers in close proximity, as shown by the controlled syntheses of early-late bimetallic (ZrIr(2) and ZrIr) and trimetallic complexes (ZrIrRh). The slow rotation of one 1,3-di-tert-butylcyclopentadienyl (Cp(tt)) ring in 1 (structure shown) allows the observation of two rotamers at room temperature. cod=1,5-cyclooctadiene. [Cp(tt)(2)Zr(µ(3)-S)(2){Ir(CO)(2)}{Rh(cod)}] 1

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The direct protonation of the bridging hydroxo ligands in [Rh(µ-OH)(1). The dinuclear framework in 1 is supported by a 1,1-cyclohexanedithiolato ligand exhibiting a 1:2κ 2 S,1:2κ 2 SЈ coordination mode. Compound 1 is an active catalyst precursor in the presence of P-donor ligands for the hydroformylation of oct-1-ene under mild conditions of pressure and temperature (100 PSI, 353 K). The best results were obtained with phosphite ligands as modifying ligands. An aldehyde selectivity of 97 %, a regioselectivity towards the linear aldehyde of 81 %, and turnover frequencies of up to 198 h -1 were