Chapter 9 - Nitrosation involving metal-nitrosyl complexes

Abstract

There is a rich chemistry involving the formation and reactions of metal–nitrosyl complexes following the earlier explosion of interest in the related metal carbonyl complexes. Much of the chemistry has been reviewed at various times. Additionally, in a recent review of many aspects of nitric oxide chemistry, there are contributions on mechanistic aspects of the reactions of nitric oxide with transition-metal complexes, non-heme iron nitrosyls in biology, and the coordination and organometallic chemistry of metal–NO complexes among others. This chapter focuses on metalnitrosyl compounds that have been used as electrophilic nitrosating agents and the nitrosation of nucleophile species coordinated to metal centers. Metal nitrosyls have been synthesized by a large variety of procedures. The common methods involve the reactions of nitric oxide, nitrous acid, nitrosyl halides, nitrosonium salts, or alkyl nitrites. Reactions can also be brought about by NO–CO ligand exchange and by the formation of nitrosyl complexes of Ru, Rh and Co using S-nitrosocysteine as the nitrosyl donor.