Reactions of low-valent metal complexes with fluorocarbons. Part XV. Acetylacetonatobis(methyldiphenyl- or triphenyl-phosphine)rhodium

Abstract

Heptafluoroiodo-n-propane and pentafluorobenzoyl chloride oxidatively add to acetylacetonatobis(methyldiphenylphosphine)rhodium to form the rhodium(III) complexes [Rh(acac)(Ph₂PMe)₂(C₃F₇)I] and [Rh(acac)(Ph₂PMe)₂(COC₆F₅)Cl]. Treatment of [Rh(L)₂(acac)] with pentafluorobenzene sulphonyl chloride affords the five-co-ordinate complexes [Rh(acac)(L)(SO₂C₆F₅)Cl](L = Ph₂PMe or Ph₃P). Tetrafluoroethylene and chlorotrifluoroethylene react with [Rh(Ph₂PMe)₂(acac)] to give respectively the rhodacyclopentane complexes [Rh(CF₂)₄(acac)(Ph₂PMe)₂] and [Rh(acac)(Ph₂PMe)₂(C₂F₃Cl)₂]. Bromotrifluoroethylene yields instead [Rh(acac)(Ph₂PMe)₂(C₂F₃Br)]. In contrast, [Rh(Ph₂PMe)₂(acac)] reacts with 1,2-dichlorotetrafluorocyclobutene to form a vinyl complex [Rh(acac)(Ph₂PMe)₂(C₄F₄Cl)Cl]. Hexafluoroacetone reacts with [Rh(Ph₂PMe)₂(acac)] to form [Rh(acac)(Ph₂PMe)₂{(CF₃)₂CO}] whereas [Rh(Ph₃P)₂(acac)] gives a five-membered ring compound (acac)(Ph₃P)[graphic omitted]. Treatment of both [Rh(Ph₂PMe)₂(acac)] and [Rh(Ph₃P)₂(acac)] with hexafluoroisopropylideneamine leads to displacement of phosphine and the formation of [Rh(acac)(L){(CF₃)₂CNH}](L = Ph₂PMe or Ph₃P). The complex [Rh(acac)(Ph₂PMe)₂{(CF₃)₂CO}] reacts with tetrafluoroethylene to give (acac)(Ph₂PMe)₂[graphic omitted].