Fluoro-complexes of platinum metals

Abstract
Metathetical reactions of AgF with chloro-complexes give the fluoro-complexes [PtF(PEt3)3][BF4], trans-[PtF(PEt3)2(PPh3)][ClO4], trans-[PtF(PEt3)2{P(OPh)3}][ClO4], [PtF(PPh3)3][BF4], [PtF(PMe2Ph)3][BF4], [PdF(PEt3)3][BF4], trans-[RhF(CO)(PPh3)2], and trans-[IrF(CO)(PPh3)2]. These products are fully characterised by 19F and 31P n.m.r. spectroscopy, and 31P n.m.r. parameters are also reported for the chloro-complexes [PtCl(PEt3)3][BF4], trans-[PtCl(PEt3)2(PPh3)][ClO4], trans-[PtCl(PEt3)2{P(OPh)3}][ClO4], and [PtCl(PPh3)3][BF4]. The results suggest that the Pt–F bonding orbital has only small contributions from the Pt 6s and F 2s orbitals. The trans influence of fluorine in these complexes is usually slightly greater than that of chlorine and the Pt–F bond is probably stronger than corresponding Pt–Cl bonds. Hydrolysis of the platinum fluorides yields hydroxo-bridged complexes, [Pt2(OH)2(PR3)4]2+, and reaction of these products with excess of tertiary phosphine gives platinum hydrides, [PtH(PR3)3]+. Reaction of [Pt(PPh3)4] with excess of anhydrous HF yields [PtF-(PPh3)3][HnFn+1](n 2–3).

This publication has 0 references indexed in Scilit: