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.