M(IV)–M′(O)-Zweikernkomplexe (M = Ti, Zr, M′ = Cr, Mo, W) mit verbrückenden Phosphinocyclopentadienid-, Chlorid- und Thiolatliganden / M(IV)–M′(O) Dinuclear Complexes (M = Ti, Zr, M′ = Cr, Mo, W) with Bridging Phosphinocyclopentadienide, Chloride, and Thiolate Ligands

Abstract

A series of ligand-bridged dinuclear complexes [MM′Cl(µ-Cl)(µ-C5H4PR2)2(CO)3] (M = Ti, Zr, M′ = Cr, Mo, W, R = C6H5, 4-C6H4CH3) was synthesized from the mononuclear precursors MCl2(C5H4PR2)2 and M′(CO)3L3. Donor ligands L cleave the chloro bridge either reversibly (L = acetonitrile) or irreversibly (L = CO, P(OMe)3) with formation of the adducts [MM′Cl2(μ-C5H4PR2)2(CO)3L]. At titanium a terminal Cl- ligand can be replaced by tBuO- whereas MeS- substitutes both terminal and bridging Cl-. The dinuclear complexes [MM′(SMe)(µ-SMe)(µ-C5H4PR2)2(CO)3] thus formed are inert towards CO or P(OMe)3.