Isocyanide complexes of rhodium and iridium. Part II. Four- and five-co-ordinate complexes containing tertiary phosphines, and some oxidative addition reactions
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, But, or p-ClC6H4; M = Ir, X = Cl, R = Pri, But, 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, But, 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(CNBut)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 = But; M = Ir, R = But, p-MeC6H4 or p-ClC6H4) were obtained by protonation of [M(CNR)3(PPh3)2]+ using HPF6. The complexes {[M(CNBut)3(PPh3)XY]Z}n(M = Rh; Z = PF6; n= 1, X = Y = l; n= 2, X = PPh3, Y = Cl, X = CNBut, 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(CNBut)3-Cll2], and [Rh{CN(p-ClC6H4)}2(C2F5)l2]2 were prepared. The RhII complexes which are probably binuclear, viz.[Rh(CNBut)3(PPh3)l]2[PF6]2 and [Rh{CN(p-ClC6H4)}2(PPh2Me)2l]2[PF6]2, are also reported.