Metal nitrido- and oxo-complexes. Part II. Osmium and ruthenium nitrido-complexes with Group 5 ligands and their reactions

Abstract

Reactions of Y[Os(N)X₄] and Y[Ru(N)Cl₄](Y = Ph₄As or Buⁿ₄N; X = Cl or Br) with arsines, stibines, and 2,2′-bipyridyl (bipy) give the nitrido-complexes [Os(N)X₃L₂] and [Ru(N)Cl₃(QPh₃)₂](L = QPh₃, AsEt₃, or ½bipy; Q = As or Sb), but tertiary phosphines give reduced species. Reaction of tertiary phosphines with [M(N)Cl₃(AsPh₃)₂](M = Os or Ru) give the phosphine imidato-complexes [M(NPR₃)Cl₃(PR₃)₂](PR₃= PPh₃, PPh₂Et, PPhEt₂, PEt₃, or PPh₂Me), and with dimethylphenylphosphine the intermediates [M(NPPhMe₂)Cl₃(AsPh₃)₂] have been isolated. Using [Os(N)Br₃(AsPh₃)₂] the complexes [Os(NPR₃)Br₃(PR₃)₂](PR₃= PPh₃, PPh₂Et, or PPhEt₂) were obtained. Oxidation of [Os(NPR₃)Cl₃(PR₃)₂] by chlorine gave the nitrides [Os(N)Cl₃(PR₃)₂]. Other new complexes which have been obtained are [Os(NHPPh₃)Cl₄(PPh₃)], [Ph₄As][OsCl₄(PPh₃)₂], [OsCl₄(PPh₃)₂], [Ph₄As][OsCl₅(PPh₃)], and [Os(OMe)₂Cl₂(PPh₃)₂]. The formation and reactions of these complexes are discussed.