Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 남원우 | * |
dc.contributor.author | 조재흥 | * |
dc.contributor.author | 이용민 | * |
dc.date.accessioned | 2016-08-28T12:08:07Z | - |
dc.date.available | 2016-08-28T12:08:07Z | - |
dc.date.issued | 2008 | * |
dc.identifier.issn | 1089-5639 | * |
dc.identifier.other | OAK-5263 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/220106 | - |
dc.description.abstract | A copper(II) complex bearing a pentadentate ligand, [Cu II(N4Py) (CF 3SO 3) 2] (1) (N4Py = N, N-bis(2- pyridylmethyl)bis(2-pyridyl)methylamine), was synthesized and characterized with various spectroscopic techniques and X-ray crystallography. A mononuclear Cu II-hydroperoxo complex, [Cu II(N4Py)(OOH)] + (2), was then generated in the reaction of 1 and H 2O 2 in the presence of base, and the reactivity of the intermediate was investigated in the oxidation of various substrates at -40 °C. In the reactivity studies, 2 showed a low oxidizing power such that 2 reacted only with triethylphosphine but not with other substrates such as thioanisole, benzyl alcohol, 1, 4-cyclohexadiene, cyclohexene, and cyclohexane. In theoretical work, we have conducted density functional theory (DFT) calculations on the epoxidation of ethylene by 2 and a [Cu III(N4Py)(O)] + intermediate (3) at the B3LYP level. The activation barrier is calculated to be 39.7 and 26.3 kcal/mol for distal and proximal oxygen attacks by 2, respectively. This result indicates that the direct ethylene epoxidation by 2 is not a plausible pathway, as we have observed in the experimental work. In contrast, the ethylene epoxidation by 3 is a downhill and low-barrier process. We also found that 2 cannot be a precursor to 3, since the homolytic cleavage of the O-O bond of 2 is very endothermic (i.e., 42 kcal/mol). On the basis of the experimental and theoretical results, we conclude that a mononuclear Cu II-hydroperoxo species bearing a pentadentate N5 ligand is a sluggish oxidant in oxygenation reactions. © 2008 American Chemical Society. | * |
dc.language | English | * |
dc.title | Combined experimental and theoretical approach to understand the reactivity of a mononuclear Cu(II)-hydroperoxo complex in oxygenation reactions | * |
dc.type | Article | * |
dc.relation.issue | 50 | * |
dc.relation.volume | 112 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 13102 | * |
dc.relation.lastpage | 13108 | * |
dc.relation.journaltitle | Journal of Physical Chemistry A | * |
dc.identifier.doi | 10.1021/jp804804j | * |
dc.identifier.wosid | WOS:000261652800047 | * |
dc.identifier.scopusid | 2-s2.0-58149164877 | * |
dc.author.google | Kamachi T. | * |
dc.author.google | Lee Y.-M. | * |
dc.author.google | Nishimi T. | * |
dc.author.google | Cho J. | * |
dc.author.google | Yoshizawa K. | * |
dc.author.google | Nam W. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | 조재흥(7403536408) | * |
dc.contributor.scopusid | 이용민(36546331100;35233855500;57192113229) | * |
dc.date.modifydate | 20240426135715 | * |