{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,3]],"date-time":"2026-06-03T04:14:51Z","timestamp":1780460091328,"version":"3.54.1"},"reference-count":70,"publisher":"Wiley","issue":"12","license":[{"start":{"date-parts":[[2006,6,20]],"date-time":"2006-06-20T00:00:00Z","timestamp":1150761600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[2006,9]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Density functional calculations are employed to investigate key intermediates of the catalytic cycle of fungal nitric oxide reductase (P450nor). The formal Fe(II)\u2013nitroxyl species Fe(II)\uf8ffNO\/(\u2212) can principally exist in the two spin\u2010states S = 0 and S = 1. In the S = 0 case, a very covalent Fe\uf8ffNO \u03c3 bond is present, which leads to an electronic structure description that is actually intermediate between Fe(I)\uf8ffNO and Fe(II)\uf8ffNO<jats:sup>\u2212<\/jats:sup>. In contrast, the S = 1 case shows a ferrous Fe(II)\uf8ffNO complex with the extra electron being stored in the \u03c0 system of the porphyrin ligand. Importantly, the Fe(II)\uf8ffNO\/(\u2212) species are very basic. The electronic structures and spectroscopic properties of the corresponding N\u2010 and O\u2010protonated forms are very different, and unequivocally show that the Mb\u2013HNO adduct (Mb\u2010Myoglobin) prepared by farmer and coworkers is in fact N\u2010protonated. The presence of an axial thiolate ligand enables a second protonation leading to the corresponding Fe(IV)\uf8ffNHOH<jats:sup>\u2212<\/jats:sup> species, which is identified with the catalytically active intermediate <jats:italic>I<\/jats:italic> of P450nor. This species reacts with a second molecule of NO by initial electron transfer from NO to Fe(IV) followed by addition of NO<jats:sup>+<\/jats:sup> forming an N\uf8ffN bond. This is accompanied by an energetically very favorable intramolecular proton transfer leading to the generation of a quite stable Fe(III)\uf8ffN(OH)(NOH) complex. This way, the enzyme is able to produce dimerized HNO under very controlled conditions and to prevent loss of this ligand from Fe(III). The energetically disfavoured tautomer Fe(III)\uf8ffN(OH<jats:sub>2<\/jats:sub>)(NO) is the catalytically productive species that spontaneously cleaves the N\uf8ffOH<jats:sub>2<\/jats:sub> bond forming N<jats:sub>2<\/jats:sub>O and H<jats:sub>2<\/jats:sub>O in a highly exergonic reaction. \u00a9 2006 Wiley Periodicals, Inc. 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