CpTiCl3(cp =η5-C5H5) in reaction with Me3SiN(H)R (R = Et, Pri, But, or Ph) yields the amido complexes cpTi(Cl)2N(H)R, which react further by HCl abstraction to give the corresponding centrosymmetric binuclear imido complexes [cp(Cl)Ti]2(µ-RN)2; substitution of the chloride ligands by organic groups is possible with the imido complexes, as is reversible reduction to stable anionic complexes.