Platinum group metal complexes of arylphosphine ligands containing perfluoroalkyl ponytails; crystal structures of [RhCl2(η5-C5Me5){P(C6H4C6F13-4)3}] and cis- and trans-[PtCl2{P(C6H4C6F13-4)3}2

Abstract

The triarylphosphine ligands PPh3–x(C6H4C6F13-4)x, x = 1, 2 or 3, reacted with [{RhCl2(η5-C5Me5)}2], [{RhCl(CO)2}2], [{IrCl(COD)}2], [PdCl2(MeCN)2] or [PtCl2(MeCN)2] to yield the complexes [RhCl2(η5-C5Me5)L] 1–3, trans-[RhCl(CO)L2] 4–6, trans-[IrCl(CO)L2] 7–9, trans-[PdCl2L2] 11–13 or cis-/trans-[PtCl2L2] 14–16 respectively. Spectroscopic studies and structural studies (EXAFS for 4–9, 11–15 and X-ray single crystal for 3 and 16) indicated that the aryl groups are fairly good insulators of the electronic influence of the perfluoroalkyl substituents whilst solubility studies indicated that at least six C6F13 units are necessary for preferential perfluorocarbon solvent solubility and that the type of metal complex is important, i.e. the Vaska’s analogues 6 and 9 are perfluorocarbon solvent soluble whereas the dichloride complexes 13 and 16 are not. Studies on the addition of dioxygen to 7–10 identified a stepwise reduction in rate following the introduction of the perfluoroalkyl ponytails.