Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 남원우 | * |
dc.date.accessioned | 2016-08-28T12:08:03Z | - |
dc.date.available | 2016-08-28T12:08:03Z | - |
dc.date.issued | 2012 | * |
dc.identifier.issn | 1549-9618 | * |
dc.identifier.other | OAK-8563 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/222448 | - |
dc.description.abstract | We present a systematic study using density functional theory (DFT) and coupled cluster (CCSD(T)) computations with an aim of characterizing a non-heme ferric-superoxo complex [(TMC)Fe(O 2)] 2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) that was proposed to perform allylic C-H activation of cyclohexene (Lee, Y.-M. et al. J. Am. Chem. Soc.2010, 132, 10668). As such, we investigated a series of iron-O 2 species without and with a sixth ligand bound to the iron ion in different O 2 coordination modes (end-on and side-on) and different spin states. Most of the iron-O 2 complexes were found to be iron(III)-superoxo species, Fe(III)(O 2 -), with high-spin (S = 5/2) or intermediate-spin (S = 3/2) ferric centers coupled ferromagnetically or antiferromagnetically to the superoxide anion radical. One iron(IV)-peroxo state, Fe(IV)(O 2 2-), was also examined. The preference for ferromagnetic or antiferromagnetic coupling modes between the superoxo and ferric radicals was found to depend on the FeOO angle, where a side-on tilt favors ferromagnetic coupling whereas the end-on tilt favors antiferromagnetic states. Experimental findings, e.g., the effects of solvent, spin state, and redox potential of non-heme Fe(II) complexes on O 2 activation, were corroborated in this work. Solvent effects were found to disfavor O 2 binding, relative to the unbound ferrous ion and O 2. The potential H-abstraction reactivity of the iron(III)-superoxo species was considered in light of the recently proposed exchange-enhanced reactivity principle (Shaik, S.; Chen, H.; Janardanan, D. Nat. Chem.2011, 3, 19). It is concluded that localization and/or decoupling of an unpaired electron in the d-block of high-spin Fe(III) center in the S = 2 and 3 ferric-superoxo complexes during H abstractions enhances exchange stabilization and may be the root cause of the observed reactivity of [(TMC)Fe(O 2)] 2+. © 2012 American Chemical Society. | * |
dc.language | English | * |
dc.title | Dioxygen activation by a non-heme iron(II) complex: Theoretical study toward understanding ferric-superoxo complexes | * |
dc.type | Article | * |
dc.relation.issue | 3 | * |
dc.relation.volume | 8 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 915 | * |
dc.relation.lastpage | 926 | * |
dc.relation.journaltitle | Journal of Chemical Theory and Computation | * |
dc.identifier.doi | 10.1021/ct300015y | * |
dc.identifier.wosid | WOS:000301396300016 | * |
dc.identifier.scopusid | 2-s2.0-84863367142 | * |
dc.author.google | Chen H. | * |
dc.author.google | Cho K.-B. | * |
dc.author.google | Lai W. | * |
dc.author.google | Nam W. | * |
dc.author.google | Shaik S. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.date.modifydate | 20240116111857 | * |