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Recent Developments in Late Metal Nitrosyl Chemistry

Driven by its biological importance, the coordination chemistry of nitric oxide (NO) has undergone a renaissance over the past 10 years. This is especially true for the late first row transition metals, including iron, cobalt, nickel, and copper. This article summarizes the literature from 2003 until the present pertaining to the synthesis and reactivity of nitrosyl complexes of these metals. Recent notable advancements in this area include the synthesis of several iron nitroxyl (NO–) complexes, as well as the development of the chemistry of dinitrosyl iron complexes (DNICs) and trinitrosyl iron complexes (TNICs). Additionally, the first structural study of a {Cu(NO)}10 nitrosyl complex was reported, and in the last 10 years several interesting transformations of bound NO involving both three- and five-coordinated nickel nitrosyl complexes have been discovered. Considerable progress has also been made toward our understanding of the redox non-innocence of the nitrosyl ligand. In particular, the electronic structure of linear metal nitrosyls has proven far more complicated than the traditional “NO+” description given to these species.