Synthesis, Structure, and Electrochemistry of Platinum(II) Metallacyclobutanes

Article abstract of DOI:10.1021/ja00372a010

The novel platinacyclobutane *CH2CH2CH2Pt*(bpy) (I) is synthesized by eiter the catodic or the chemical reduction of the readily available platinum(IV) analogue *CH2CH2CH2Pt*(bpy)Cl2.X-ray crystallography reveals the essential identity of the platinacyclobutane moiety in both the platinum(II) and platinum(IV) derivatives.Unlike the platinum(IV) metallacyclobutane, however, the platinacycle I readily undergoes the replacement of α,α'-bipyridine (bpy) by various monodentate ligands such as tert-butyl isocyanide and phosphines, and insertion into the Pt-C bond by sulfur and carbon monoxide, to afford a series of new organoplatinim(II) complexes.The oxidation and reduction of the various platinum(II) metallacyclobutanes and their derivatives are explored with cyclic voltammetric techniques.The ESR spectra of the paramagnetic platinum(I) anions derived from the cathodic and chemical reduction of the platinacyclobutane I and its derivatives are reported.