Prediction of the Reduction Potential of tris(2,2 '-bipyridinyl) Iron(III/II) Derivatives

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The reduction potentials of a tris(2,2-bipyridinyl)iron (III/II) and iron(III/II) couples complexed with 2,2-bipyridinyl derivatives in acetonitrile are predicted using density functional theory. The calculation protocol proposed by Kim et al. (Kim, J. Park, Y. S. Lee, J. Comput. Chem. 2013, 34, 2233) showing reliable performance for the reduction potential is used. The four kinds of the functional groups, a methoxy group, a methyl group, a chlorine atom, and a cyanide group, are substituted at the ligands to examine the electronic effect on the reduction potential. Electron donating/withdrawing effect is analyzed by comparing the reduction potential having different substituents at the same position. The influence of the geometrical strain on the reduction potential is investigated. The good correlation between the experimental results and the calculated results is obtained. Not only the general trend, but also the detailed phenomena are correctly reproduced. The maximum deviation from the experimental value is 0.083 V for the methyl substitution at the position 4. The mean absolute error for the seven couples is 0.047 V. The difference of the reduction potential between the chlorine atom substituted at the positions 4 and 5, 0.1 V, is well described. The difference between the CN and the Cl substitution of 0.318 and 0.228 V for the position 4 and 5 is correctly obtained as 0.325 and 0.213 V, respectively. The simple linear relation between the lowest unoccupied molecular orbital (LUMO) energy of the Fe(III) complexes in solution and the calculated reduction potentials is obtained with the R-2 of 0.977.
Publisher
WILEY-BLACKWELL
Issue Date
2015-01
Language
English
Article Type
Article
Keywords

ELECTRON-WITHDRAWING SUBSTITUENTS; DENSITY-FUNCTIONAL THEORY; REDOX POTENTIALS; METAL-COMPLEXES; IRON COMPLEXES; BATTERIES; DESIGN; RUTHENIUM(II); OXIDATION; COUPLE

Citation

JOURNAL OF COMPUTATIONAL CHEMISTRY, v.36, no.1, pp.33 - 41

ISSN
0192-8651
DOI
10.1002/jcc.23766
URI
http://hdl.handle.net/10203/195107
Appears in Collection
CH-Journal Papers(저널논문)
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