GENERALIZED MOLECULAR-ORBITAL CALCULATIONS ON TRANSITION-METAL DIOXYGEN COMPLEXES - MODEL FOR MANGANESE PORPHYRIN Academic Article

abstract

• Restricted Hartree-Fock plus configuration interaction and generalized molecular orbital plus configuration interaction calculations are reported for several structural models of the dioxygen complexes of manganese(II) porphyrins. An analysis of the results suggests a ground-state structure with a side-on (Griffith) dioxygen and oxygen atoms eclipsing the ring nitrogens. The calculation predicts three singly occupied metal orbitals (t22e1 in pseudocubic symmetry; 111 in pseudolinear symmetry) in agreement with the ESR results. In contrast to previous ab initio calculations, the CI results also predict a ground-state end-on (Pauling) structure with three unpaired electrons in metal orbitals that would be consistent with the ESR. On the basis of our calculations alone, this structure could not be eliminated as a possibility. 1985, American Chemical Society. All rights reserved.

authors

• Hall, Michael

published proceedings

• INORGANIC CHEMISTRY

author list (cited authors)

• NEWTON, J. E., & HALL, M. B.

citation count

• 14

complete list of authors

• NEWTON, JE||HALL, MB

publication date

• July 1985

publisher

• American Chemical Society (ACS)  Publisher

published in

• Inorganic Chemistry  Journal

Digital Object Identifier (DOI)

• 10.1021/ic00210a022

start page

• 2573

end page

• 2577

volume

• 24

issue

• 16

URL

• http://dx.doi.org/10.1021/ic00210a022