Reactions of Metal Nitrosyl Complexes

The NO/NO+ and NO/NO- self-exchange rates are quite slow (42). Therefore, the kinetics of nitric oxide electron transfer reactions are strongly affected by transition metal complexes, particularly by those that are labile and redox active which can serve to promote these reactions. Although iron is the most important metal target for nitric oxide in mammalian biology, other metal centers might also react with NO. For example, both cobalt (in the form of cobalamin) (43,44) and copper (in the form of different types of copper proteins) (45) have been identified as potential NO targets. In addition, a substantial fraction of the bacterial nitrite reductases (which catalyze reduction of NO2 to NO) are copper enzymes (46). The interactions of NO with such metal centers continue to be rich for further exploration. 

The NO reduction of the Cu(II) complex Cu(dmp)2(H20)2+ (dmp = 2,9-dimethyl-l,10-phenanthroline) to give Cu(dmp)2 plus nitrite ion (Eq. (20)) has been studied in aqueous solution and various mixed solvents (42a). The reduction potential for Cu(dmp)2(H20)2+ (0.58 V vs. NHE in water) (48) is substantially more positive than those for most cupric complexes owing to steric repulsion between the 2,9-methyl substituents that provide a bias toward the tetrahedral coordination of Cu(I). The less crowded bis(l,10-phenanthroline) complex Cu(phen)2(H20)2+ is a weaker oxidant (0.18 V) (48). 

The kinetics of this reaction were followed by tracking the appearance of Cu(dmp)J at 455 nm, the A,max of the metal to ligand charge transfer (MLCT) absorption band. At a fixed pH, the kinetics in aqueous solution followed the rate law 

Addition of NaN02 (50 pM) had no effect on the reaction profile with NO present, and no reaction was observed (on the time scale of the stopped-flow experiment) when NO was absent. However, at higher concentrations, anions, including the conjugate bases of various buffers (B ), slowed down the reaction. This was attributed to the competition between water and the anions for the labile 5th coordination site of Cu(dmp)2(H20)2+. 

These results can be analyzed in the context of two different mechanisms. The first would be simple outer-sphere electron transfer to give Cu(I) plus NO+ followed by hydrolysis of the latter (Eqs. (22) and (23)). 

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