Fluoro-complexes of iridium and platinum.

A range of low-valent iridium and platinum fluoro-complexes have been prepared and characterized by a combination of mass spectrometry, 19F 31P{lcub}1H{rcub}, 195Pt{lcub}1H{rcub} and infrared spectroscopies and EXAFS where possible. [Dichlorobis(amine)platinum(II)] complexes of the type [PtCl2(L)2] (L = NMe3, NH3, py; L2 = en, bipy) have been reacted with [XeF2], undergoing oxidative fluorination, to afford various isomers of platinum(IV) amine-fluoride species. The presence of anhydrous hydrofluoric acid (AHF) was observed to influence the nature of the products formed whilst the cis- or trans- stereochemistry of the starting materials was found to determine the number of isomers formed. The first unambiguously characterized difluorobis(phosphine)-platinum(II) complex, cis-[PtF2(PEt3)2] was formed from the reaction of cis-[PtMe2(PEt3)2] and AHF with the elimination of methane gas being the driving force for the reaction. The difluoro-complex, is stable only in AHF or under vacuum, it was characterized by low-temperature 195Pt{lcub}1H{rcub} NMR spectroscopy. Analogues of Vaska's complex of the type, trans-[IrCl(CO)(PR3)2] (PR3 = PPh3, Pcy3) have been shown to undergo oxidative fluorination reactions with [XeF2] resulting in the formation of cis-, trans-[IrF2Cl(CO)(PR3)2]. Furthermore, the reaction between fluoro-Vaska's trans- [IrF(CO)(PPh3)2] and [XeF2] has been found to afford the novel trifluoro-complex mer-,trans-[IrF3(CO)(PPh3)2]. A series of complexes of the type mer-, [IrF3(CO)(L)2] (L = tertiary phosphine, amine or arsine) have been prepared from the reaction of fac-[IrF3(CO)3] and the appropriate Lewis base. The amine and arsine derivatives represent the first examples of fluoroiridium(III) amine or arsine complexes. X-ray crystal structure determinations for the complexes trans- [PtCl2(NMe3)2], [Pt(C6H4PPh2)(PPh3)2][SbF6], trans-[Ir(C6F5)(CO){lcub}PPh2(C6F5)2{rcub}2] and [HNEt3][PtCl3(NEt3)] are described.