Electronic structures of the Compound I (CpdI) in P450 are investigated on the basis of spin coupling forms of iron-oxo (Fe(IV)O) cores and radical ligand (•L) groups to generalize previous singlet and triplet diradical (TD) mechanisms for oxygenations of alkanes with Fe( IV)O. Orbital interaction schemes for four lower-lying spin configurations of CpdI with HC bond of substrate are examined to elucidate how magnetic coupling modes correlate with radical reaction pathways for hydroxylation reactions on the basis of the broken symmetry (BS) molecular orbital (MO) model. The configuration correlation diagrams for the four configurations model are depicted on the basis of the isoelectronic analogy among O, O2, and Fe( IV)O, in addition to Coulomb exchange energy on the iron site, which determines its local spin configuration. Important role of ligand spin (•L) of CpdI for regulation of hydroxylation mechanisms is clarified with the aid of the spin coupling forms. Transition states for one quartet and three doublet configurations under the BS MO approximation are examined on the basis of potential curve crossings along reaction pathways. The four transition structures and corresponding radical intermediates for methane and trimethyl methane with CpI are located by the BS hybrid Kohn–Sham density functional theory (DFT) (B3LYP) method to confirm the orbital interaction schemes. Spin density populations obtained by the BS B3LYP calculations are found to be consistent with the theoretical predictions based on the four configurations model. The configuration and state correlation diagrams by BS B3LYP before and after spin projection are also consistent with the BS MO interaction schemes, which provide local SD and TD mechanisms of hydroxylation with CpdI. The present BS MO-theoretical framework is useful for systematic understanding of a lot of recent BS hybrid DFT computational results for hydroxylation reactions with CpdI and configuration correlation diagrams reported by several groups. Implications of the present theoretical and computational results are discussed in relation to several experimental characteristics of hydroxylation reactions with iron-oxo species and P450. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009
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