Study of the phenanthroline-Mn-imidazole bonding in Mn(I) triscarbonyl complex: A X-ray and DFT computational analysis

Author(s)

de Aguiar, Inara ^[1] ; Lima, Francisco C. A. ^[2] ; Ellena, Javier ^[3] ; Malta, Valeria R. S. ^[4] ; Carlos, Rose M. ^[1]

Affiliation

^[1] Univ Fed Sao Carlos, Dept Quim, BR-13565905 Sao Carlos, SP - Brazil

^[2] Univ Estadual Piaui, Dept Quim, Ctr Ciencias Nat, BR-64002150 Teresina - Brazil

^[3] Univ Sao Paulo, Inst Fis Sao Carlos, BR-13560905 Sao Carlos, SP - Brazil

^[4] Univ Fed Alagoas, Inst Quim & Biotecnol, BR-57072970 Maceio, AL - Brazil

• Document type: Journal article
• Source: COMPUTATIONAL AND THEORETICAL CHEMISTRY; v. 965, n. 1, p. 7-14, APR 2011.
• Web of Science Citations: 3

Abstract

355 nm light irradiation of fac-{[}Mn(CO)(3)(phen)(imH)](+) (fac-1) produces the mer-1 isomer and a long lived radical which can be efficiently trapped by electron acceptor molecules. EPR experiments shows that when excited, the manganese(I) complex can be readily oxidized by one-electron process to produce Mn(II) and phen(.-). In the present study, DFT calculations have been used to investigated the photochemical isomerization of the parent Mn(I) complex and to characterize the electronic structures of the long lived radical. The theoretical calculations have been performed on both the fac-1 and mer-1 species as well as on their one electron oxidized species fac-1+ and mer-1+ for the lowest spin configurations (S = 1/2) and fac-6 and mer-6 (S = 5/2) for the highest one to characterize these complexes. In particular, we used a charge decomposition analysis (CDA) and a natural bonding orbital (NBO) to have a better understanding of the chemical bonding in terms of the nature of electronic interactions. The observed variations in geometry and bond energies with an increasing oxidation state in the central metal ion are interpreted in terms of changes in the nature of metal-ligand bonding interactions. The X-ray structure of fac-1 is also described. (C) 2011 Elsevier B.V. All rights reserved. (AU)

• FAPESP's process: 09/08218-0 - New Mn(I)-photosentizer complexes: mimicking the electron donor side of photosystem II in artificial photosynthesis
• Grantee: Rose Maria Carlos
• Support Opportunities: Regular Research Grants