Volume 32, Issue 1

Compared to the overwhelming prevalence of f-element-carbon, -nitrogen, -oxygen or -halide ligand linkages, the use of metal-based fragments as ligands is underdeveloped. This contrasts directly to the extensively developed fields of d- and p-block metal-metal complexes, which are still burgeoning. This review outlines the development of compounds that possess polarised covalent f-element-metal bonds. For this review, the f-element is defined as (i) a group 3 metal; (ii) a lanthanide metal; (iii) the actinide metals thorium or uranium. The metal is defined as: (i) a d-block transition metal; (ii) a group 13 metal (aluminium or gallium); (iii) a group 14 metal (silicon, germanium or tin); (iv) a group 15 metal (antimony or bismuth) metal. Although silicon, germanium and antimony are traditionally classified as metalloids, they are included for completeness. We focus on complexes that have been structurally authenticated by single crystal X-ray diffraction, and we highlight novel aspects of their syntheses, properties and reactivities.

This review covers over 110 monomeric Pt(0) organometallics and 220 monomeric Pt(II) organometallics. The predominant geometry for Pt(0) is square planar, with some examples of two-, five-, and six-coordinated. The monomeric Pt(II) organometallics in the review covers only those with the chromophores PtC 4 , PtA 3 B and PtC 2 A 2 . The most common ligand, besides C donor ligands, which are of a wide variety, is PPh 3 . At least two types of isomerism occur in the platinum organometallics analysed in this review: cis - trans and distortion. Relations between Pt-ligand bond distances, bond angles and trans effect are discussed regarding steric and electronic influence.