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.
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