Isocyanide complexes of rhodium and iridium. Part II. Four- and five-co-ordinate complexes containing tertiary phosphines, and some oxidative addition reactions

Abstract

The synthesis of [Rh(CNR)₂(PR′₃)₂][PF₆](R′= Ph, R = Me, Prⁱ, or p-ClC₆H₄; R′₃= Ph₂Me, R = Prⁱ or p-ClC₆H₄), [Rh(CNR)(PPh₂Me)₃][PF₆](R = Prⁱ or p-ClC₆H₄), [M(CNR)₃(PR′₃)₂]X (M = Rh, X = PF₆, R = Prⁱ, Bu^t, or p-ClC₆H₄; M = Ir, X = Cl, R = Prⁱ, Bu^t, p-MeC₆H₄, or p-ClC₆H₄), [Rh(CNR)₂(PR′₃)₃][PF₆](R′= Ph, R = Me or p-ClC₆H₄; R′₃= Ph₂Me, R = Me, Prⁱ, Bu^t, or p-ClC₆H₄), [Ir(CO)(CNPrⁱ)₂(PPh₃)₂]Cl, [Rh(CNR)(CNR′)₂(PPh₃)₂][PF₆](R = Prⁱ, R′=p-ClC₆H₄; R =p-ClC₃H₄, R′= Prⁱ) and [Rh(CNBu^t)_4–(PPh₃)][PF₆], from [M(CO)(PPh₃)₂Cl](M = Rh or Ir), [Rh(PPh₂Me)₃L][PF₆](L = CO or PPh₂Me), or [Rh(CNR)₄][PF₆], as precursors, is described. The hydrides, [M(CNR)₃(PPh₃)₂H][PF₆]₂(M = Rh, R = Bu^t; M = Ir, R = Bu^t, p-MeC₆H₄ or p-ClC₆H₄) were obtained by protonation of [M(CNR)₃(PPh₃)₂]⁺ using HPF₆. The complexes {[M(CNBu^t)₃(PPh₃)XY]Z}_n(M = Rh; Z = PF₆; n= 1, X = Y = l; n= 2, X = PPh₃, Y = Cl, X = CNBu^t, Y = Me; M = Ir; Z = Cl, n= 1, X = PPh₃, Y = SO₂, or CS₂; Z = Cl, n= 2, X = PPh₃, Y = SnPh₃; Z = BPh₄, n= 2, X = PPh₃, Y = C₃H₅; Z = PF₆, n= 1, X = C₃H₅, Y = Cl, n= 2, X = PPh₃, Y = OMe), [Rh{CN-(p-ClC₆H₄)}₂(PPh₂Me)₂Cl₂][PF₆], [Ir(CNPiⁱ)₂(PPh₃)₂XY]Cl (X = Cl, T = SnPh; X = I, Y = Me), [Rh(CNBu^t)_3-Cll₂], and [Rh{CN(p-ClC₆H₄)}₂(C₂F₅)l₂]₂ were prepared. The Rh^II complexes which are probably binuclear, viz.[Rh(CNBu^t)₃(PPh₃)l]₂[PF₆]₂ and [Rh{CN(p-ClC₆H₄)}₂(PPh₂Me)₂l]₂[PF₆]₂, are also reported.