Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Shunichi Fukuzumi | * |
dc.date.accessioned | 2016-08-28T12:08:08Z | - |
dc.date.available | 2016-08-28T12:08:08Z | - |
dc.date.issued | 2011 | * |
dc.identifier.issn | 0002-7863 | * |
dc.identifier.other | OAK-7878 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/221879 | - |
dc.description.abstract | A coordinatively saturated ruthenium(II) complex having tetradentate tris(2-pyridylmethyl)amine (TPA) and bidentate 2,2′-bipyridine (bpy), [Ru(TPA)(bpy)] 2+ (1), was oxidized by a Ce(IV) ion in H 2O to afford a Ru(IV)-oxo complex, [Ru(O)(H +TPA)(bpy)] 3+ (2). The crystal structure of the Ru(IV)-oxo complex 2 was determined by X-ray crystallography. In 2, the TPA ligand partially dissociates to be in a facial tridentate fashion and the uncoordinated pyridine moiety is protonated. The spin state of 2, which showed paramagnetically shifted NMR signals in the range of 60 to -20 ppm, was determined to be an intermediate spin (S = 1) by the Evans' method with 1H NMR spectroscopy in acetone-d 6. The reaction of 2 with various oraganic substrates in acetonitrile at room temperature afforded oxidized and oxygenated products and a solvent-bound complex, [Ru(H +TPA)(bpy)(CH 3CN)], which is intact in the presence of alcohols. The oxygenation reaction of saturated C-H bonds with 2 proceeds by two-step processes: the hydrogen abstraction with 2, followed by the dissociation of the alcohol products from the oxygen-rebound complexes, Ru(III)-alkoxo complexes, which were successfully detected by ESI-MS spectrometry. The kinetic isotope effects in the first step for the reaction of dihydroanthrathene (DHA) and cumene with 2 were determined to be 49 and 12, respectively. The second-order rate constants of C-H oxygenation in the first step exhibited a linear correlation with bond dissociation energies of the C-H bond cleavage. © 2011 American Chemical Society. | * |
dc.language | English | * |
dc.title | Formation of a ruthenium(IV)-oxo complex by electron-transfer oxidation of a coordinatively saturated ruthenium(II) complex and detection of oxygen-rebound intermediates in C-H bond oxygenation | * |
dc.type | Article | * |
dc.relation.issue | 30 | * |
dc.relation.volume | 133 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 11692 | * |
dc.relation.lastpage | 11700 | * |
dc.relation.journaltitle | Journal of the American Chemical Society | * |
dc.identifier.doi | 10.1021/ja2037645 | * |
dc.identifier.wosid | WOS:000293872800050 | * |
dc.identifier.scopusid | 2-s2.0-79960872441 | * |
dc.author.google | Kojima T. | * |
dc.author.google | Nakayama K. | * |
dc.author.google | Ikemura K. | * |
dc.author.google | Ogura T. | * |
dc.author.google | Fukuzumi S. | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.date.modifydate | 20240401081001 | * |