Abstract
Treatment of TiCl 4(dmpe) ( 1a) and TiCl 4(depe) ( 1b) with two equivalents of C 3H 5MgCl in toluene at −30°C affords two novel allyl–titanium complexes: a dinuclear mixed-valent Ti 2 5+ species Ti 2(μ-Cl) 2Cl 2(dmpe) 2(μ 2-η 3-C 3H 5) ( 2) and a mononuclear Ti III complex, TiCl(depe)(η 3-C 3H 5) 2 ( 3). Syntheses and crystal structures of 1b, 2 and 3 are presented. In complex 2, in addition to two bridging chloride ligands a η 3-allyl group spans two titanium atoms with a Ti…Ti separation of 2.908(1) Å. The allyl bridge is symmetrical with each terminal carbon atom having a Ti–C distance of 2.154(6) Å, while the central carbon atom is equidistant from the titanium atoms, Ti–C cent, 2.430(6) Å. Each Ti atom in 2 is further coordinated by a chelating dmpe ligand and a chloride ion. In the mononuclear complex 3 two η 3-allyl groups are bound to the Ti III center and the coordination is completed by a chelating diphosphine ligand and one chloride ion. The Ti–C distances in 3 vary from 2.286(3) to 2.478(3) Å.
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