Copper(I) complexations and their reaction with nitrite ion

CHED 1105

Sarah Meade, smeade512@hawks.rwu.edu and Stephen K. O'Shea, soshea@rwu.edu. Department of Chemistry, Roger Williams University, Roger Williams University Box 5071, One Old Ferry Road, Bristol, RI 02809
Consumption of nitrate-contaminated water can lead to its conversion to nitrite in the stomach. Nitrite can go onto react with oxyhemoglobin to form methemoglobin releasing NO. The physiological mechanism for this reaction can be elucidated through biomemetic modeling of the interaction of nitrite with other biometals. This research investigated the reaction of nitrite ion with chelated Cu(I) complexed species [TMPA, dipyridyl, acetate, pyridine]. A postulated intermediate Cu(I) nitrite complex reacts to form a copper nitrosyl complex with concomitant oxidation of triphenyl phospine(TPP). Varying redox potentials are conveyed to the active copper center by the coordination of ligands. This influences the rates of reaction and Cu-NO complex stability. Increased reaction rates positively influence the ease of redox. The strength of Cu-NO bond has been determined by FTIR. 31P NMR confirmed quantitative formation of the TPP oxide. Kinetic rates for the formation of Cu(I) nitrosyl was determined by UV-vis spectroscopy.