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Following up on the characterization of a new (heme)Fe III -superoxide species formed from the cryogenic oxygenation of a ferrous-heme (P Py )Fe II ( 1 ) (P Py = a tetraarylporphyrinate with a covalently tethered pyridine group as a potential axial base), giving (P Py )Fe III -O 2  •- ( 2 ) ( Li Y et al., Polyhedron 2013; 58 : 60-64), we report here on (i) its use in forming a cytochrome c oxidase (C c O) model compound, or (ii) in a reaction with nitrogen monoxide (•NO; nitric oxide) to mimic nitric oxide dioxygenase (NOD) chemistry. Reaction of ( 2 ) with the cuprous chelate [Cu I (AN)][B(C 6 F 5 ) 4 ] (AN = bis[3-(dimethylamino) propyl]amine) gives a meta -stable product [(P Py )Fe III -([Formula: see text])-Cu II (AN)][B(C 6 F 5 )4] ( 3a ), possessing a high-spin iron(III) and Cu(II) side-on bridged peroxo moiety with a μ-η 2 :η 2 -binding motif. This complex thermally decays to a corresponding μ-oxo complex [(P Py )Fe III -(O 2- )-Cu II (AN)][B(C 6 F 5 )4] ( 3 ). Both ( 3 ) and ( 3a ) have been characterized by UV-vis, 2 H NMR and EPR spectroscopies. When ( 2 ) is exposed to •NO (g) , a ferric heme nitrato compound forms; if 2,4-di- tert -butylphenol is added prior to •NO (g) exposure, phenol ortho -nitration occurs with the iron product being the ferric hydroxide complex (P Py ) Fe III (OH) ( 5 ). The latter reactions mimic the action of NOD's.

Reactions of a heme-superoxo complex toward a cuprous chelate and •NO(g):CcOand NOD chemistry

Reactions of a heme-superoxo complex toward a cuprous chelate and •NO_(g):CcOand NOD chemistry