{"created":"2023-07-27T06:26:50.983378+00:00","id":10741,"links":{},"metadata":{"_buckets":{"deposit":"78dca929-8936-4f1e-a01d-34a8cd87c28d"},"_deposit":{"created_by":3,"id":"10741","owners":[3],"pid":{"revision_id":0,"type":"depid","value":"10741"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00010741","sets":["934:935:937"]},"author_link":["16392","54","16391","15267","10605","16389","16390","16393","2561","1738"],"item_4_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2004-01-01","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"1","bibliographicPageEnd":"72","bibliographicPageStart":"59","bibliographicVolumeNumber":"77","bibliographic_titles":[{"bibliographic_title":"Bulletin of the Chemical Society of Japan"}]}]},"item_4_creator_33":{"attribute_name":"著者別表示","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"古舘, 英樹"}],"nameIdentifiers":[{},{}]},{"creatorNames":[{"creatorName":"藤波, 修平"}],"nameIdentifiers":[{},{}]},{"creatorNames":[{"creatorName":"鈴木, 正樹"}],"nameIdentifiers":[{},{},{}]}]},"item_4_description_21":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"Oxygenation of copper(I) with tetradentate tripodal ligands (L) comprised of a tris(aminoethyl)amine (tren) skeleton having sterically bulky substituent(s) on the terminal nitrogens has been investigated, where L = tris(N-benzylaminoethyl)amine (LH,Bn), tris(N-benzyl-N-methylaminoethyl)amine (LMe,Bn), or tris(N,N-dimethylaminoethyl)amine (LMe,Me). All the copper(I) complexes reacted with dioxygen at low temperatures to produce superoxocopper(II) and/or trans-(μ-1,2-peroxo)-dicopper(II) complexes depending on the steric bulkiness of the terminal nitrogens and the reaction conditions. The reaction of a copper(I) complex [Cu(LH,Bn)]+ at −90 °C in acetone resulted in the formation of a superoxo complex [Cu(LH,Bn)(O2)]+ as a less stable species and a peroxo complex [{Cu(LH,Bn)}2(O2)]2+ as a stable species. The structures of [Cu(LH,Bn)]ClO4 and [{Cu(LH,Bn)}2(O2)](BPh4)2·8(CH3)2CO were determined by X-ray crystallography. [{Cu(LH,Bn)}2(O2)]2+ has a trans-(μ-1,2-peroxo)-dicopper(II) core with a trigonal bipyramidal structure. The O–O bond distance is 1.450(5) Å with an intermetallic Cu···Cu separation of 4.476(2) Å. The resonance Raman spectrum of [{Cu(LH,Bn)}2(O2)]2+ measured at −90 °C in acetone-d6 showed a broad ν(O–O) band at 837–834 cm−1 (788 cm−1 for an 18O labeled sample) and two ν(Cu–O) bands at 556 and 539 cm−1, suggesting the presence of two peroxo species in solution. [Cu(LMe,Bn)]+ also produced both superoxo and trans-μ-1,2-peroxo species, [Cu(LMe,Bn)(O2)]+ and [{Cu(LMe,Bn)}2(O2)]2+. At a lower concentration of [Cu(LMe,Bn)]+ (∼0.24 mM) and higher dioxygen concentration (P(O2) = ∼1 atm), the superoxo species is predominantly formed, whereas at a higher concentration of [Cu(LMe,Bn)]+ (∼1 mM) and lower dioxygen concentration (P(O2) = ∼0.02 atm) the formation of the peroxo species is observed. The resonance Raman spectrum of [Cu(LMe,Bn)(O2)]+ (∼1 mM) in acetone-d6 at ∼−95 °C exhibited a ν(O–O) band at 1120 cm−1 (1059 cm−1 for an 18O labeled sample) and that of [{Cu(LMe,Bn)}2(O2)]2+ (∼3 mM) in acetone-d6 at ∼−90 °C showed two ν(O–O) bands at 812 and 797 cm−1 (767 and 753 cm−1 for an 18O labeled sample), respectively. A similar observation was also made for [{Cu(LMe,Me)}2(O2)]2+. Relationships between the energies of the LMCT and d–d transitions and those of the ν(O–O) and ν(Cu–O) stretching vibrations and the steric constraints in the Cu(II)–(O22−)–Cu(II) core are discussed.","subitem_description_type":"Abstract"}]},"item_4_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00010728","subitem_identifier_reg_type":"JaLC"}]},"item_4_publisher_17":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"The Chemical Society of Japan = 日本化学会"}]},"item_4_relation_12":{"attribute_name":"DOI","attribute_value_mlt":[{"subitem_relation_type":"isIdenticalTo","subitem_relation_type_id":{"subitem_relation_type_id_text":"10.1246/bcsj.77.59","subitem_relation_type_select":"DOI"}}]},"item_4_relation_28":{"attribute_name":"関連URI","attribute_value_mlt":[{"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://www.jstage.jst.go.jp/browse/bcsj","subitem_relation_type_select":"URI"}},{"subitem_relation_type_id":{"subitem_relation_type_id_text":"http://www.chemistry.or.jp/","subitem_relation_type_select":"URI"}}]},"item_4_rights_23":{"attribute_name":"権利","attribute_value_mlt":[{"subitem_rights":"Copyright © The Chemical Society of Japan 日本化学会"}]},"item_4_source_id_11":{"attribute_name":"NCID","attribute_value_mlt":[{"subitem_source_identifier":"AA00580132","subitem_source_identifier_type":"NCID"}]},"item_4_source_id_9":{"attribute_name":"ISSN","attribute_value_mlt":[{"subitem_source_identifier":"0009-2673","subitem_source_identifier_type":"ISSN"}]},"item_4_version_type_25":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_970fb48d4fbd8a85","subitem_version_type":"VoR"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"Komiyama, Kazuya"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Furutachi, Hideki"}],"nameIdentifiers":[{},{},{}]},{"creatorNames":[{"creatorName":"Nagatomo, Shigenori"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Hashimoto, Akifumi"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Hayashi, Hideki"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Fujinami, Shuhei"}],"nameIdentifiers":[{},{},{}]},{"creatorNames":[{"creatorName":"Suzuki, Masatatsu"}],"nameIdentifiers":[{},{},{}]},{"creatorNames":[{"creatorName":"Kitagawa, Teizo"}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2017-10-03"}],"displaytype":"detail","filename":"SC-PR-SUZUKI-M-59.pdf","filesize":[{"value":"510.7 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-SUZUKI-M-59.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/10741/files/SC-PR-SUZUKI-M-59.pdf"},"version_id":"e480bcf2-028e-4048-9ac9-51a789c6a312"}]},"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":"Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes"}]},"item_type_id":"4","owner":"3","path":["937"],"pubdate":{"attribute_name":"公開日","attribute_value":"2017-10-03"},"publish_date":"2017-10-03","publish_status":"0","recid":"10741","relation_version_is_last":true,"title":["Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes"],"weko_creator_id":"3","weko_shared_id":3},"updated":"2023-07-27T11:28:34.011821+00:00"}