Crystallographic and structural characterization of heterometallic platinum clusters Part VIII. Heteronona- and heterodecanuclear clusters

Abstract

Abstract This review classifies and analyses fifty heteronona- and heterodecanuclear Pt clusters of metal composition: Pt4Ru5, Pt3Ru6, Pt20sr PtRh8, PtAu8; Pt6M4, Pt5M5, Pt4M6, Pt3M2, Pt2M8, PtM9, Pt3Ru6M and PtAu8M. There are nine different heterometals: M = Ru, Au, Ag, Cu, Hg, Os, Rh, Ir and Fe, of which Ru and Au are the most frequent. The clusters crystallize mostly into two crystal classes, monoclinic (74%) and triclinic (18%), and their structures are complex. Three triangular layers of nine metal atoms arranged in the form of a face-shared bioctahedron are common in the series of heterononanuclear clusters. In the series of heterodecanuclear clusters distorted skeletal icosahedrons, where a central platinum atom is surrounded by nine metal atoms, and face (edge) shared (fused) bioctahedral cluster of the metal atoms are the most common. The most frequent ligands are CO and PPh3. The shortest metal-metal bond distances are: 2.540(4) Å (Pt-Fe), 2.580(2) Å (Ru-Ru), 2.584 Å (Pt-Pt) and 2.629(4) Å (Cu-Au). Several relationships between the structural parameters were found and are discussed. Some clusters contain two crystallographically independent molecules within the same crystal and are examples of distortion isomerism.