View : 15 Download: 0

Correlating DFT-calculated energy barriers to experiments in nonheme octahedral FeIVO species

Title
Correlating DFT-calculated energy barriers to experiments in nonheme octahedral FeIVO species
Authors
Cho K.-B.Kim E.J.Seo M.S.Shaik S.Nam W.
Ewha Authors
남원우서미숙
SCOPUS Author ID
남원우scopus
Issue Date
2012
Journal Title
Chemistry - A European Journal
ISSN
0947-6539JCR Link
Citation
vol. 18, no. 33, pp. 10444 - 10453
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
The experimentally measured bimolecular reaction rate constant, k 2, should in principle correlate with the theoretically calculated rate-limiting free energy barrier, ΔG≠, through the Eyring equation, but it fails quite often to do so due to the inability of current computational methods to account in a precise manner for all the factors contributing to ΔG≠. This is further aggravated by the exponential sensitivity of the Eyring equation to these factors. We have taken herein a pragmatic approach for C-H activation reactions of 1,4-cyclohexadiene with a variety of octahedral nonheme FeIVO complexes. The approach consists of empirically determining two constants that would aid in predicting experimental k2 values uniformly from theoretically calculated electronic energy (ΔE≠) values. Shown in this study is the predictive power as well as insights into energy relationships in Fe IVO C-H activation reactions. We also find that the difference between ΔG≠ and ΔE≠ converges at slow reactions, in a manner suggestive of changes in the importance of the triplet spin state weight in the overall reaction. Useful correlations: Seven different synthetic nonheme FeIVO species were investigated with both theoretical and experimental methods in order to obtain a statistical base from which useful predictions and insights can be made (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOI
10.1002/chem.201200096
Appears in Collections:
자연과학대학 > 화학·나노과학전공 > Journal papers
Files in This Item:
There are no files associated with this item.
Export
RIS (EndNote)
XLS (Excel)
XML


qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE