Charge distribution in Mn(salen) complexes
Article first published online: 4 JAN 2014
Copyright © 2014 Wiley Periodicals, Inc.
International Journal of Quantum Chemistry
Volume 114, Issue 8, pages 525–533, 15 April 2014
How to Cite
How to cite this article: Int. J. Quantum Chem. 2014, 114, 525–533. DOI: 10.1002/qua.24604, , , , .
- Issue published online: 3 MAR 2014
- Article first published online: 4 JAN 2014
- Manuscript Accepted: 16 DEC 2013
- Manuscript Revised: 13 DEC 2013
- Manuscript Received: 15 NOV 2013
- Fundação para a Ciência e Tecnologia (FCT). Grant Numbers: PEst-C/EQB/LA0006/2011, Projects PTDC/CTM-NAN/112241/2009 and NORTE-07–0124-FEDER-000067—NANOCHEMISTRY, SFRH/BD/64314/2009 (F.T.)
- density functional theory;
- effective atomic charges;
- population analysis
The charge and spin distribution in manganese-salen complexes were analyzed using different basis sets and density functionals. Five population analysis methods [Mulliken, Löwdin, Natural population analysis (NPA), atoms in molecules (AIM), and CHelpG] were used to characterize the charge distribution. Results show that NPA and AIM were the only methods capable of giving charges with the correct sign for all cases under study. According to the analysis of the natural charge and spin distributions, the salen ligand shows a complex behavior, counteracting the effect of the chloro and oxo ligands on the metal center. Furthermore, the presence of a chloride counter ion increases the oxo-radical character of Oxo-Mn(salen) complexes, which may play an important role in the rationalization of the catalytic properties of Mn(salen) complexes. © 2014 Wiley Periodicals, Inc.