Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | 서미숙 | * |
dc.date.accessioned | 2016-08-28T10:08:34Z | - |
dc.date.available | 2016-08-28T10:08:34Z | - |
dc.date.issued | 2012 | * |
dc.identifier.issn | 0947-6539 | * |
dc.identifier.other | OAK-9074 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/222893 | - |
dc.description.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. | * |
dc.language | English | * |
dc.title | Correlating DFT-calculated energy barriers to experiments in nonheme octahedral FeIVO species | * |
dc.type | Article | * |
dc.relation.issue | 33 | * |
dc.relation.volume | 18 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 10444 | * |
dc.relation.lastpage | 10453 | * |
dc.relation.journaltitle | Chemistry - A European Journal | * |
dc.identifier.doi | 10.1002/chem.201200096 | * |
dc.identifier.wosid | WOS:000307108100037 | * |
dc.identifier.scopusid | 2-s2.0-84864587790 | * |
dc.author.google | Cho K.-B. | * |
dc.author.google | Kim E.J. | * |
dc.author.google | Seo M.S. | * |
dc.author.google | Shaik S. | * |
dc.author.google | Nam W. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.date.modifydate | 20240116111857 | * |