PMID- 26056423 OWN - NLM STAT- PubMed-not-MEDLINE LR - 20240323 IS - 1088-4246 (Print) IS - 1099-1409 (Electronic) IS - 1088-4246 (Linking) VI - 19 IP - 1-3 DP - 2015 Jan-Mar TI - Reactions of a heme-superoxo complex toward a cuprous chelate and *NO((g)): CcO and NOD chemistry. PG - 352-360 AB - 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 (CcO) 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 mu-eta(2):eta(2)-binding motif. This complex thermally decays to a corresponding mu-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. FAU - Sharma, Savita K AU - Sharma SK AD - Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA. FAU - Rogler, Patrick J AU - Rogler PJ AD - Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA. FAU - Karlin, Kenneth D AU - Karlin KD AD - Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA. LA - eng GR - R01 GM060353/GM/NIGMS NIH HHS/United States PT - Journal Article PL - Singapore TA - J Porphyr Phthalocyanines JT - Journal of porphyrins and phthalocyanines JID - 9890997 PMC - PMC4457333 MID - NIHMS692072 OTO - NOTNLM OT - heme-copper-mu-oxo OT - heme-superoxo OT - high spin heme-copper peroxo OT - nitrate OT - peroxynitrite EDAT- 2015/06/10 06:00 MHDA- 2015/06/10 06:01 PMCR- 2016/01/01 CRDT- 2015/06/10 06:00 PHST- 2015/06/10 06:00 [entrez] PHST- 2015/06/10 06:00 [pubmed] PHST- 2015/06/10 06:01 [medline] PHST- 2016/01/01 00:00 [pmc-release] AID - 10.1142/S108842461550025X [doi] PST - ppublish SO - J Porphyr Phthalocyanines. 2015 Jan-Mar;19(1-3):352-360. doi: 10.1142/S108842461550025X.