Fluorophosphine complexes of ruthenium and osmium. Part 4. Homo-binuclear trichloro-bridged complexes of ruthenium(II)

Abstract

The reaction of [RuCl₂(PPh₃)₃] with different mol ratios of PF₃ proceeds via the trichloro-bridged binuclear complexes [(Ph₃P)₂(F₃P) RuCl₃RuCl(PPh₃)₂] and [(Ph₃P)₂(F₃P) RuCl₃RuCl(PF₃)(PPh₃)] to form the stable mononuclear complex via-[ RuCl₂(PF₃)₂(PPh₃)₂]. Similar reactions occur with PF₂(NMe₂). The binuclear complexes have been isolated and characterised by ¹⁹F and ³¹P n.m.r. spectroscopy. The cis-[ RuCl₂L₂(PPh₃)₂] complexes [L = PF₃ or PF₂(NMe₂)] react with [RuCl₂(PPh₃)₂] to form the trichloro-bridged dimers [(Ph₃P)₂(F₃P)RuCl₃RuCl-(PF₃)(PPh₃)] and [(Ph₃P){(Me₂N) F₂P}₂RuCl₃RuCl(PPh₃)₂] respectively. Syntheses of [(Ph₃P)₂(OC) RuCl₃-RuCl(PF₃)(PPh₃)], [(Ph₃P)₂(OC)RuCl₃RuCl(CO)(PPh₃)], and cis-[RuCl₂(CO)(PF₃)(PPh₃)₂] are also reported. Possible mechanisms for the formation of the dimeric complexes are discussed and some reactions are reported.