{"created":"2021-03-01T07:11:30.487824+00:00","id":32779,"links":{},"metadata":{"_buckets":{"deposit":"9c78dbaf-301f-48b6-a88a-824480669452"},"_deposit":{"id":"32779","owners":[],"pid":{"revision_id":0,"type":"depid","value":"32779"},"status":"published"},"_oai":{"id":"oai:tsukuba.repo.nii.ac.jp:00032779","sets":["117:1207","117:1706","117:2918","3:62:5298:2018"]},"item_5_biblio_info_6":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2015-02","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"2","bibliographicPageEnd":"955","bibliographicPageStart":"945","bibliographicVolumeNumber":"6","bibliographic_titles":[{"bibliographic_title":"Chemical science "}]}]},"item_5_creator_3":{"attribute_name":"著者別名","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"小谷, 弘明"}],"nameIdentifiers":[{},{},{}]},{"creatorNames":[{"creatorName":"石塚, 智也"}],"nameIdentifiers":[{},{},{}]},{"creatorNames":[{"creatorName":"小島, 隆彦"}],"nameIdentifiers":[{},{},{}]}]},"item_5_description_4":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"A mononuclear Cr(V)–oxo complex, [CrV(O)(6-COO−-tpa)](BF4)2 (1; 6-COO−-tpa = N,N-bis(2-pyridylmethyl)-N-(6-carboxylato-2-pyridylmethyl)amine) was prepared through the reaction of a Cr(III) precursor complex with iodosylbenzene as an oxidant. Characterization of 1 was achieved using ESI-MS spectrometry, electron paramagnetic resonance, UV-vis, and resonance Raman spectroscopies. The reduction potential (Ered) of 1 was determined to be 1.23 V vs. SCE in acetonitrile based on analysis of the electron-transfer (ET) equilibrium between 1 and a one-electron donor, [RuII(bpy)3]2+ (bpy = 2,2′-bipyridine). The reorganization energy (λ) of 1 was also determined to be 1.03 eV in ET reactions from phenol derivatives to 1 on the basis of the Marcus theory of ET. The smaller λ value in comparison with that of an Fe(IV)–oxo complex (2.37 eV) is caused by the small structural change during ET due to the dπ character of the electron-accepting LUMO of 1. When benzyl alcohol derivatives (R-BA) with different oxidation potentials were employed as substrates, corresponding aldehydes were obtained as the 2e−-oxidized products in moderate yields as determined from 1H NMR and GC-MS measurements. One-step UV-vis spectral changes were observed in the course of the oxidation reactions of BA derivatives by 1 and a kinetic isotope effect (KIE) was observed in the oxidation reactions for deuterated BA derivatives at the benzylic position as substrates. These results indicate that the rate-limiting step is a concerted proton-coupled electron transfer (PCET) from substrate to 1. In sharp contrast, in the oxidation of trimethoxy-BA (Eox = 1.22 V) by 1, trimethoxy-BA radical cation was observed by UV-vis spectroscopy. Thus, it was revealed that the mechanism of the oxidation reaction changed from one-step PCET to stepwise ET–proton transfer (ET/PT), depending on the redox potentials of R-BA.","subitem_description_type":"Abstract"}]},"item_5_publisher_27":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"The Royal Society of Chemistry"}]},"item_5_relation_11":{"attribute_name":"DOI","attribute_value_mlt":[{"subitem_relation_type_id":{"subitem_relation_type_id_text":"10.1039/C4SC02285H ","subitem_relation_type_select":"DOI"}}]},"item_5_rights_12":{"attribute_name":"権利","attribute_value_mlt":[{"subitem_rights":"© The Royal Society of Chemistry 2015. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence."}]},"item_5_select_15":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_select_item":"author"}]},"item_5_source_id_7":{"attribute_name":"ISSN","attribute_value_mlt":[{"subitem_source_identifier":" 2041-6520  ","subitem_source_identifier_type":"ISSN"}]},"item_5_source_id_9":{"attribute_name":"書誌レコードID","attribute_value_mlt":[{"subitem_source_identifier":"AA12555653","subitem_source_identifier_type":"NCID"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"Kotani,  Hiroaki"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Kaida, Suzue "}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Ishizuka, Tomoya "}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Sakaguchi, Miyuki "}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Ogura, Takashi "}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Shiota,  Yoshihito"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Yoshizawa, Kazunari "}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Kojima,   Takahiko"}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2015-03-11"}],"displaytype":"detail","filename":"CS_6-2.pdf","filesize":[{"value":"1.5 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"CS_6-2.pdf ","url":"https://tsukuba.repo.nii.ac.jp/record/32779/files/CS_6-2.pdf"},"version_id":"52209242-c42d-4545-bb6d-c232ffd06323"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"journal article","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"Formation and characterization of a reactive chromium(V)–oxo complex: mechanistic insight into hydrogen-atom transfer reactions","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Formation and characterization of a reactive chromium(V)–oxo complex: mechanistic insight into hydrogen-atom transfer reactions"}]},"item_type_id":"5","owner":"1","path":["1706","1207","2918","2018"],"pubdate":{"attribute_name":"公開日","attribute_value":"2015-03-10"},"publish_date":"2015-03-10","publish_status":"0","recid":"32779","relation_version_is_last":true,"title":["Formation and characterization of a reactive chromium(V)–oxo complex: mechanistic insight into hydrogen-atom transfer reactions"],"weko_creator_id":"1","weko_shared_id":5},"updated":"2022-04-27T09:01:03.331351+00:00"}