Electrophilic behaviour of the co-ordinated nitrosyl cation: reactions of pentahalogenonitrosyliridate(1–)
Abstract
The complexes [Ir(X)5NO]–(X = Cl or Br) are attacked at the nitrosyl nitrogen atom by nucleophiles according to the equations: (i)[Ir(X)5NO]–+ 2OH–⇌[Ir(X)5NO2]3–+ H2O; (ii)[Ir(X)5NO]–+ NH2OH →[Ir(X)5H2O]2–+ N2O + H+; (iii)[Ir(X)5NO]–+ N3–+ H2O →[Ir(X)5H2O]2–+ N2O + N2; and (iv)[Ir(X)5NO]–+ 2NH3→[Ir(X)5NH3]2–+ N2+ H3O+. Hydrazine hydrate and [Ir(Br)5NO]– form [IrBr3(N2H4)3],0·5H2O by an unknown route. Equilibrium constants for the reversible reaction with OH– are compared with the analogous reactions of NO+ and [Fe(CN)5NO]2–.