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Performing Organic Chemistry with Inorganic Compounds: Electrophilic Reactivity of Selected Nitrosyl Complexes

Fabio Doctorovich* and Florencia Di Salvo

Departamento de Química Inorgánica, Analítica y Química Física/INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, piso 3, C1428EHA Buenos Aires, Argentina

Acc. Chem. Res., 2007, 40 (10), pp 985–993

DOI: 10.1021/ar6000457

Publication Date (Web): September 6, 2007

* To whom correspondence should be addressed. E-mail: doctorovich@qi.fcen.uba.ar.

Biography

Fabio Doctorovich was born in Buenos Aires, Argentina, in 1961. He received his Ph.D. degree from the University of Buenos Aires in 1990. Following five years of postdoctoral training at the Georgia Institute of Technology, he became Professor at the Department of Inorganic, Analytical and Physical Chemistry at the University of Buenos Aires. His main research interests include investigations on NO and HNO chemistry, dealing with organic compounds, nitrosyl complexes, and metalloporphyrins.

Biography

Florencia Di Salvo obtained her M.Sc. in chemistry from the University of Buenos Aires in 2003. She is currently completing her Ph.D. thesis on electrophilic reactions of nitrosyl complexes with aliphatic amines, under the supervision of Fabio Doctorovich.

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 Ir^IV–NO^• instead of Ir^III–NO⁺ (as for the K⁺ and Na⁺ salts).