Organic chemistry of inorganic complexes: electrophilic reactivity of [IrCl5NO]– and group VIII nitrosyl complexes. Some unusual structural features

DOCTOROVICH,* F.; DI SALVO, F.

ACCOUNTS OF CHEMICAL RESEARCH

ACS Publications

Año: 2007 vol. 40 p. 985 - 993

0001-4842

ABSTRACT The inorganic nitrosyl (NO+) complexes [Fe(CN)5NO]2-, [Ru(bpy)2 (NO)Cl]2+, and [IrCl5(NO)]- are useful reagents for the nitrosation of a variety of organic compounds, ranging from amines to the relatively inert alkenes. Regarding [IrCl5(NO)]-, its high electrophilicity and inertness define it as a unique reagent and provide a powerful synthetic route for the isolation and stabilization of coordinated nitroso compounds that are unstable in free form, such as S-nitrosothiols and primary nitrosamines. Related to the high electrophilicity of [IrCl5(NO)]-, an unusual behavior is described for its PPh4 + salt in the solid state, showing an electronic distribution represented by IrIV–NO• instead of IrIII–NO+ (as for the K+ and Na+ salts).+) complexes [Fe(CN)5NO]2-, [Ru(bpy)2 (NO)Cl]2+, and [IrCl5(NO)]- are useful reagents for the nitrosation of a variety of organic compounds, ranging from amines to the relatively inert alkenes. Regarding [IrCl5(NO)]-, its high electrophilicity and inertness define it as a unique reagent and provide a powerful synthetic route for the isolation and stabilization of coordinated nitroso compounds that are unstable in free form, such as S-nitrosothiols and primary nitrosamines. Related to the high electrophilicity of [IrCl5(NO)]-, an unusual behavior is described for its PPh4 + salt in the solid state, showing an electronic distribution represented by IrIV–NO• instead of IrIII–NO+ (as for the K+ and Na+ salts).