The chemistry of transition-metal nitrosyl compounds. Part VII. The preparation and study of some cationic nitrosyl complexes of iron

Abstract

The cationic iron nitrosyl complexes [Fe(CO)₂NOL₂]PF₆[L = P(OPh)₃, P(OMe)₃, PPh₃, PMePh₂, PMe₂Ph, PEt₃, P(C₆H₁₁)₃, AsPh₃ and 1/2dppe] have been prepared and some of their properties studied. Certain of these cations [L = P(OMe)₃, PMePh₂, and PMe₂Ph] react with additional ligand (L) to produce the cationic species [Fe(CO)(NO)L₃]⁺. With dppe the complex [Fe(CO)₂NO(dppe)]PF₆ yields the mononitrosyl cation [Fe(NO)(dppe)₂]⁺; this cation has also been prepared from the reaction of the hydride FeHCl(dppe)₂ with N-methyl-N-nitrosotoluene-p-sulphonamide in the presence of NaBPh₄. The cations [Fe(CO)₂NOL₂]⁺ react with OMe^– to produce the neutral carboxy-compounds Fe(CO)(NO)(L)₂CO₂Me (L = PPh₃ or 1/2dppe). No evidence for nucleophilic addition of OMe^– to the co-ordinated NO group in any of the cationic species has been found.