An unusual early-late bimetallic complex with direct metal-metal bonding is obtained from a phosphinoenolate ligand-assisted reaction between Ti(IV) and Pt(0) reagents which occurs by formal insertion of the Pt(0) centre into a Ti(IV)-O bond; X-ray data and EHMO calculations indicate the presence of a quasi-covalent Ti(III)-Pt(I) bond (2.721(2) A).