Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | 조재흥 | * |
dc.date.accessioned | 2016-08-28T10:08:31Z | - |
dc.date.available | 2016-08-28T10:08:31Z | - |
dc.date.issued | 2013 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.other | OAK-9818 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223486 | - |
dc.description.abstract | The geometric and electronic structures and reactivity of an S = 5/2 (HS) mononuclear nonheme (TMC)FeIII-OOH complex are studied by spectroscopies, calculations, and kinetics and compared with the results of previous studies of S = 1/2 (LS) FeIII-OOH complexes to understand parallels and differences in mechanisms of O-O bond homolysis and electrophilic H-atom abstraction reactions. The homolysis reaction of the HS [(TMC)FeIII-OOH]2+ complex is found to involve axial ligand coordination and a crossing to the LS surface for O-O bond homolysis. Both HS and LS FeIII-OOH complexes are found to perform direct H-atom abstraction reactions but with very different reaction coordinates. For the LS FeIII-OOH, the transition state is late in O-O and early in C-H coordinates. However, for the HS FeIII-OOH, the transition state is early in O-O and further along in the C-H coordinate. In addition, there is a significant amount of electron transfer from the substrate to the HS FeIII-OOH at transition state, but that does not occur in the LS transition state. Thus, in contrast to the behavior of LS FeIII-OOH, the H-atom abstraction reactivity of HS FeIII-OOH is found to be highly dependent on both the ionization potential and the C-H bond strength of the substrate. LS FeIII-OOH is found to be more effective in H-atom abstraction for strong C-H bonds, while the higher reduction potential of HS FeIII-OOH allows it to be active in electrophilic reactions without the requirement of O-O bond cleavage. This is relevant to the Rieske dioxygenases, which are proposed to use a HS FeIII-OOH to catalyze cis-dihydroxylation of a wide range of aromatic compounds. © 2013 American Chemical Society. | * |
dc.language | English | * |
dc.title | Comparison of high-spin and low-spin nonheme FeIII-OOH complexes in O-O bond homolysis and H-atom abstraction reactivities | * |
dc.type | Article | * |
dc.relation.issue | 8 | * |
dc.relation.volume | 135 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 3286 | * |
dc.relation.lastpage | 3299 | * |
dc.relation.journaltitle | Journal of the American Chemical Society | * |
dc.identifier.doi | 10.1021/ja400183g | * |
dc.identifier.wosid | WOS:000315618900064 | * |
dc.identifier.scopusid | 2-s2.0-84874631578 | * |
dc.author.google | Liu L.V. | * |
dc.author.google | Hong S. | * |
dc.author.google | Cho J. | * |
dc.author.google | Nam W. | * |
dc.author.google | Solomon E.I. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | 조재흥(7403536408) | * |
dc.date.modifydate | 20240116111857 | * |