Über den „Neuanbindungs”-Mechanismus der Alkanhydroxylierung durch Cytochrom P450: elektronische Struktur der Zwischenstufe und Charakter des Elektronentransfers bei der Neuanbindung

Der Mechanismus der Alkanhydroxylierung [1] durch Cytochrom P450 wirft interessante Fragen auf. Nach dem allgemein akzeptierten Mechanismus [2] (Schema 1) erfolgt im Schema 1. Schematische Darstellung des Wiederanbindungs-Mechanismus.Schema 2. a) Orbitaldiagramme der Low-Spin-und High-Spin-Kopplung des Hydroxoeisen-Komplexes im Triplettzustand mit dem Alkylradikal im Wiederanbindungsschritt. b) Die Elektronenverschiebung beim Auffüllen des ¹Lochsª im a 2u -Orbital des Porphyrinrestes.

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Zwei Reaktionswege beim „Wiederanbindungs”-Mechanismus der Alkanhydroxylierung durch Cytochrom P450: Entstehung freier Radikale mit begrenzter Lebensdauer

Harris

Cohen

Filatov

et al. 2000

Angewandte Chemie

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How Does Ethene Inactivate Cytochrome P450 En Route to Its Epoxidation? A Density Functional Study

2001

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What Is the Difference between the Manganese Porphyrin and Corrole Analogues of Cytochrome P450's Compound I?

Visser¹,

Ogliaro²,

Gross³

et al. 2001

Chem. Eur. J.

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Density functional calculations on oxo-manganese complexes of corrole (1) and porphyrin (2 and 3) show a fundamental difference. The ground state of I is the singlet manganese(V) state, 1A(MnV), in which corrole is a closed shell. In contrast, 2 and 3 have high-spin manganese(IV) states, 1A1u and 3A2u respectively. This difference and the state ordering for each system are rationalized based on the competition between the intrinsic tendency of manganese to prefer high-spin electronic configurations, vis-à-vis the general tendency to prefer double occupancy in the low-lying orbitals. The outcome of this competition is determined primarily by the identity of the macrocycle, corrole versus porphyrin. Corrole with a small cavity holds the MnO moiety with a high off-plane displacement, and thereby prefers the low-spin state. On the other hand, porphyrin with the wider cavity holds the MnO moiety closer to the plane, and thereby prefers high-spin states.

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Über den „Neuanbindungs”-Mechanismus der Alkanhydroxylierung durch Cytochrom P450: elektronische Struktur der Zwischenstufe und Charakter des Elektronentransfers bei der Neuanbindung

Cited by 12 publications

References 23 publications

Zwei Reaktionswege beim „Wiederanbindungs”-Mechanismus der Alkanhydroxylierung durch Cytochrom P450: Entstehung freier Radikale mit begrenzter Lebensdauer

Zwei Reaktionswege beim „Wiederanbindungs”-Mechanismus der Alkanhydroxylierung durch Cytochrom P450: Entstehung freier Radikale mit begrenzter Lebensdauer

How Does Ethene Inactivate Cytochrome P450 En Route to Its Epoxidation? A Density Functional Study

What Is the Difference between the Manganese Porphyrin and Corrole Analogues of Cytochrome P450's Compound I?

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