Reactions of low-valent metal complexes with fluorocarbons. Part XXIV. Chloronitrosylbis(triphenyl-, methyldiphenyl- and dimethylphenyl-phosphine)ruthenium and nitrosyltris(triphenylphosphine)iridium

Abstract

Tetrafluoroethylene and hexafluorobut-2-yne react with RuCl(NO)L₂(L = PPh₃, PMePh₂, PMe₂Ph) to form the complexes [R[graphic omitted]F₂(Cl)(NO)L₂] and [R[graphic omitted](CF₃)(Cl)(NO)L₂] respectively; the phosphine ligands have a relative trans-configuration. Chlorotrifluoroethylene and hexafluoropropene react with RuCl(NO)(PMe₂Ph)₂ to form adducts in which the phosphine ligands have a relative cis-configuration. Iodine adds trans to RuCl(NO)(PMePh₂) to form Rul₂Cl(NO)(PMePh₂) which isomerises in solution. Nitrosyltris(triphenylphosphine)iridium reacts with CF₃CCCF₃ to form di-µ-hexafluorobut-2-enylene-bis[cis-triphenylphosphine(nitrosyl)iridium(I)], whereas tetrafluoroethylene and hexafluoroacetone form [I[graphic omitted]F₂(NO)(PPh₃)₂] and [I[graphic omitted](NO)(PPh₃)]. The ruthenium hexafluorobut-2-yne complexes undergo ring-opening reactions with CF₃CO₂H to form vinyl complexes.