Crystallographic and structural characterization of heterometallic platinum complexes Part VI. Heterohexanuclear complexes

AbstractThis review classifies and analyzes heterohexanuclear platinum clusters into seven types of metal combinations:Pt5M, Pt4M2, Pt3M3, Pt2M4, PtM5, Pt2M3M′, and Pt2M2M2′. The crystals of these clusters generally belong to six crystal classes: monoclinic, triclinic, orthorhombic, tetragonal, trigonal and cubic. Among the wide range of stereochemistry adopted by these clusters, octahedral and capped square-pyramidal are the most common. Although platinum is classified as a soft metal atom, it bonds to a variety of soft, borderline and hard metals. Nineteen different heterometal ions are involved in hexanuclear platinum clusters. The shortest Pt-M bond distance in the case of M being a non-transition element is 2.395(4) Å for germanium and for M being a transition metal ion it is 2.402(2) Å for Cobalt. The shortest Pt-Pt bond distance observed in these clusters is 2.532 Å. Several relationships between the structural parameters are identified and discussed. Some clusters exist in two isomeric forms and some show crystallographically independent molecules within the same crystal. Such isomers and independent molecules are examples of distortion isomerism.