Spectroscopic studies of the interaction of cobalt(II) N,N',N″,N‴-tetramethyltetra-3,4-pyridinoporphyrazine with amino acids and nitrogen oxides

Abstract

The interaction of histidine, cysteine, NO and nitrite with cobalt(II) N,N',N″,N‴-tetramethyltetra-3,4-tetrapyridinoporphyrazine ([ Co II tmtppa ]4+) is reported. Metal-based autoreduction of [ Co II tmtppa ]4+ occurs with the formation of the [ Co I tmtppa (-2)]3+ species in the presence of histidine and cysteine. Kinetic data for the auto reduction of [ Co II tmtppa ]4+ in the presence of these amino acids gave the rate constants k f = 2.1 × 101 and 2.8 dm3 mol-1 s-1, for cysteine and histidine, respectively. One molecule of NO or nitrite was found to coordinate to the [ Co II tmtppa ]4+ species. The equilibrium and rate constants for the coordination of the nitric oxide were K = 2.3 × 104 dm 3 mol -1 and k f = 7.5 dm 3 mol -1 s -1, respectively. The coordination of nitrite to [ Co II tmtppa ]4+ occurred with an equilibrium constant of K = 2.0 × 102 dm 3 mol -1 and a rate constant of k f = 4.0 × 10-3 dm 3 mol -1 s -1. There was no evidence for the coordination of two molecules of nitrite to the [ Co II tmtppa ]4+ species.