Solution decomposition of platinum(II) fluoride cations; single-crystal structure of [Pt(PPh3)2(C6H4PPh2)][SbF6]·CD2Cl2

Abstract

An extended X-ray absorption fine structure (EXAFS) investigation of the metal co-ordination geometry in the cations [PtF(PR₃)₃]⁺ (R = Et or Ph) indicates that the Pt–F bond lengths are identical and only slightly longer than those typical for low-valent metal fluoride complexes. The solution decomposition of the complexes, [PtF(PPh₃)₃][X] (X = HF₂, BF₄ or SbF₆), have been studied in both wet and dry chlorinated solvents and the only reactions observed have been due to the presence of water, producing, initially, [Pt(OH)(PPh₃)₃]⁺ and subsequently the ortho-metallated products [Pt(PPh₃)₃(C₆H₄PPh₂)][X], which have been characterised by mass spectrometry, multinuclear NMR spectroscopy and, when X = SbF₆, by single-crystal X-ray crystallography.