What is the difference between the manganese porphyrin and corrole analogues of cytochrome P450's compound I?

Sam P. De Visser, François Ogliaro, Zeev Gross*, Sason Shaik

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

87 Scopus citations

Abstract

Density functional calculations on oxo-manganese complexes of corrole (1) and porphyrin (2 and 3) show a fundamental difference. The ground state of 1 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, 3A1u 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.

Original languageEnglish
Pages (from-to)4954-4960
Number of pages7
JournalChemistry - A European Journal
Volume7
Issue number22
DOIs
StatePublished - 19 Nov 2001

Keywords

  • Density functional calculations
  • Metalloenzymes
  • Oxomanganese corrole
  • Oxomanganese porphyrin

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