Mechanisms of Nitric Oxide Reactions Mediated by Biologically Relevant Metal Centers

摘要: Struct Bond (2014) 154: 99–136 DOI: 10.1007/430_2013_117 # Springer-Verlag Berlin Heidelberg 2013 Published online: 5 October Mechanisms of Nitric Oxide Reactions Mediated by Biologically Relevant Metal Centers Peter C. Ford, Jose Clayston Melo Pereira, and Katrina M. Miranda Abstract Here, we present an overview mechanisms relevant to the formation several key reactions nitric oxide (nitrogen monoxide) complexes with biologically metal centers. The focus will be largely on iron copper complexes. We discuss applications both thermal photochemical methodologies for investigating such quantitatively. Keywords Copper Heme models Hemes Iron Metalloproteins Contents Introduction . Metal-Nitrosyl Bonding How Does Coordinated Nitrosyl Affect Center? Formation Decay Nitrosyls 4.1 Some General Considerations 4.2 Rates NO Models 4.3 Mechanistic Studies “On” “Off” 4.4 Non-Heme Complexes 4.5 Other Biological Interest Reductive Nitrosylation 5.1 Iron(III) Nucleophiles 5.2 Reduction Copper(II) 5.3 Protonation 5.4 Dioxygen 6 Summary References P.C. Ford ( * ) J.C.M. Pereira Department Chemistry Biochemistry, University California, Santa Barbara, CA 93106-9510, USA e-mail: ford@chem.ucsb.edu K.M. Arizona, Tucson, AZ, kmiranda@email.arizona.edu