The unique chemistry of platina-β-diketones

Abstract

This review presents syntheses, structures and the reactivity of platina-β-diketones [Pt₂{(COR)₂H}₂(µ-Cl)₂] (R = alkyl, ω-phenylalkyl), being the first electronically unsaturated (16 ve; ve-valence electrons) and kinetically labile metalla-β-diketones. They were found to react with amines, yielding platina-β-diketonates of platina-β-diketones having Pt₄ zigzag chains analogous to platinum blue complexes. Reactions of platina-β-diketones with monodentate and bidentate N-, P-, As-, O-, and S-donor ligands are described resulting in the formation of acyl(hydrido)platinum(IV) complexes, acyl(chloro)platinum(II) complexes, platinum complexes having enamine–amide type ligands, and of platinum(II) complexes with cyclic aminocarbene ligands, respectively. These reactions are discussed in terms of oxidative addition and reductive elimination reactions showing that platina-β-diketones react as hydroxycarbene complexes whose OH groups are intramolecularly hydrogen-bridged to acyl ligands. Furthermore, the synthesis and structures of dinuclear platinum(II) complexes with bridging µ-acyl(hydroxycarbene) ligands are presented.