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 | 2041-6520 | * |
dc.identifier.other | OAK-9813 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223481 | - |
dc.description.abstract | Mononuclear metal-dioxygen adducts, such as metal-superoxo and -peroxo species, are generated as key intermediates in the catalytic cycles of dioxygen activation by heme and non-heme metalloenzymes. We have shown recently that the geometric and electronic structure of the Ni-O2 core in [Ni(n-TMC)(O2)]+ (n = 12 and 14) varies depending on the ring size of the supporting TMC ligand. In this study, mononuclear Ni(ii)-superoxo and Ni(iii)-peroxo complexes bearing a common macrocylic 13-TMC ligand, such as [NiII(13-TMC)(O2)]+ and [NiIII(13-TMC)(O2)]+, were synthesized in the reaction of [NiII(13-TMC)(CH3CN)]2+ and H 2O2 in the presence of tetramethylammonium hydroxide (TMAH) and triethylamine (TEA), respectively. The Ni(ii)-superoxo and Ni(iii)-peroxo complexes bearing the common 13-TMC ligand were successfully characterized by various spectroscopic methods, X-ray crystallography and DFT calculations. Based on the combined experimental and theoretical studies, we conclude that the superoxo ligand in [NiII(13-TMC)(O 2)]+ is bound in an end-on fashion to the nickel(ii) center, whereas the peroxo ligand in [NiIII(13-TMC)(O 2)]+ is bound in a side-on fashion to the nickel(iii) center. Reactivity studies performed with the Ni(ii)-superoxo and Ni(iii)-peroxo complexes toward organic substrates reveal that the former possesses an electrophilic character, whereas the latter is an active oxidant in nucleophilic reaction. This journal is © The Royal Society of Chemistry 2013. | * |
dc.language | English | * |
dc.title | Mononuclear nickel(ii)-superoxo and nickel(iii)-peroxo complexes bearing a common macrocyclic TMC ligand | * |
dc.type | Article | * |
dc.relation.issue | 4 | * |
dc.relation.volume | 4 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 1502 | * |
dc.relation.lastpage | 1508 | * |
dc.relation.journaltitle | Chemical Science | * |
dc.identifier.doi | 10.1039/c3sc22173c | * |
dc.identifier.wosid | WOS:000315597900013 | * |
dc.identifier.scopusid | 2-s2.0-84874611770 | * |
dc.author.google | Cho J. | * |
dc.author.google | Kang H.Y. | * |
dc.author.google | Liu L.V. | * |
dc.author.google | Sarangi R. | * |
dc.author.google | Solomon E.I. | * |
dc.author.google | Nam W. | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.contributor.scopusid | 조재흥(7403536408) | * |
dc.date.modifydate | 20240116111857 | * |