Interactions of Nitrosoalkanes/arenes, Nitrosamines, Nitrosothiols, and Alkyl Nitrites with Metals

This chapter focuses attention on the interactions of four types of organo-NOx (x= 1) compounds with metals. It describes the chemistry of C-nitroso compounds, N-nitroso compounds, S-nitroso compounds, and O-nitroso compounds. Nitrosoalkanes and nitrosoarenes frequently serve as ligands to metal centers, and in many cases simple adduct formation between the pre-formed C-nitroso compounds and metal centers occur with or without the displacement of an existing ligand on the metal. The chapter presents the synthetic routes to metal-nitrosoalkane and metal-nitrosoarene compounds and the binding modes of the C-nitroso ligands that have been established crystallographically. It examines the fundamental coordination chemistry of these organonitroso compounds with metal centers that form the basis for their observed chemical and biochemical reactivity. Adsorption of alkyl nitrites on metal surfaces frequently results in the generation of alkoxy radicals and NO, and can lead to follow-up reactions with other substrates.