期刊
CANADIAN JOURNAL OF CHEMISTRY
卷 87, 期 7, 页码 1063-1073出版社
CANADIAN SCIENCE PUBLISHING
DOI: 10.1139/V09-037
关键词
porphyrins; transition -metal complexes; aromaticity; density functional theory
资金
- Spanish research projects [CTQ2008-03077/BQU, CTQ2008-06532/BQU]
- DURSI [2005SGR-00238]
- Spanish MICINN [AP2005-2997]
- ICREA Funding Source: Custom
We report here the chemical bonding and aromaticity patterns in metalloporphyrins, which were obtained with density functional theory (DFT) calculations at the OPBE/TZP level. This level of theory was previously shown to be very accurate for determining spin-state splittings [J. Chem. Theory Comput. 2008, 4, 2057] of transition-metal complexes. We considered metalloporphyrins along the first-row transition metals (Sc-Zn) extended with alkaline-earth metals (Mg, Ca) and several second-row transition metals (Ru, Pd, Ag, Cd). An energy decomposition analysis was performed to study the metal-ligand interactions, which showed that almost all complexes are significantly stabilized through (covalent) orbital interactions. The only exception is with calcium as the central metal, which interacts with the porphyrin mainly through electrostatic interactions. Furthermore, we studied aromaticity patterns for these complexes by looking at a number of (structural and electronic) aromaticity descriptors, for both the inner-ring and outer-ring of the porphyrin and of the pyrroles. The inner-ring (N16) aromaticity is shown to be unaffected by metal complexation, while the outer-ring (N20) and the pyrrole (N5) aromaticities are found to increase significantly in the metal coordinated porphyrins.
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