{"created":"2023-07-27T06:26:51.193361+00:00","id":10746,"links":{},"metadata":{"_buckets":{"deposit":"5f134ec8-35cc-43b4-bf88-878fe2ffb96f"},"_deposit":{"created_by":3,"id":"10746","owners":[3],"pid":{"revision_id":0,"type":"depid","value":"10746"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00010746","sets":["934:935:937"]},"author_link":["16402","49959","54","16401","10605","15876","1738","16400","16403"],"item_4_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1998-01-01","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"10","bibliographicPageEnd":"2279","bibliographicPageStart":"2267","bibliographicVolumeNumber":"71","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":"藤波, 修平"}],"nameIdentifiers":[{},{}]},{"creatorNames":[{"creatorName":"鈴木, 正樹"}],"nameIdentifiers":[{},{},{}]},{"creatorNames":[{"creatorName":"上原, 章"}],"nameIdentifiers":[{},{}]}]},"item_4_description_21":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"A new dinucleating ligand containing a sterically bulky imidazolyl group, Ph-Htidp (N,N,N′,N′-tetrakis[(1-methyl-4,5-diphenyl-2-imidazolyl)methyl]-1,3-diamino-2-propanol), and its μ-alkoxo-diiron(II) complexes [Fe2(Ph-tidp)(RCO2)](ClO4)2, (RCO2 = C6H5CO2 (1), C6F5CO2 (2), CF3CO2 (3), and C2H5CO2 (4)), were synthesized. The structure of complex 1 was determined by X-ray crystallography. Complex 1 crystallizes in the monoclinic space group P21/c with a = 13.464(2), b = 19.223(4), c = 31.358(4) Å, β = 92.84(2)°, and Z = 4. The complex has a doubly-bridged structure with μ-alkoxo of Ph-tidp and μ-benzoate; the two iron centers have a distorted five-coordinate structure with N3O2 donor set. All the complexes showed fairly good reversible oxygenation below −30 °C in CH2Cl2, which was monitored by UV-vis and NMR spectroscopies, and dioxygen up-take measurements. Introduction of 4,5-diphenyl substituents into 2-imidazolyl group stabilized the μ-peroxo diiron species against irreversible oxidation, just as introduction of 6-methyl substituent into 2-pyridyl group did. Phenyl substituents appear to weaken the electron donor ability of a dinucleating ligand to stabilize divalent oxidation state of iron and to form a hydrophobic cavity for a O2 binding site, which would suppress the irreversible oxidation and facilitate the reversible oxygenation. Dioxygen affinities of the Ph-tidp and Me4-tpdp diiron(II), and the tpdp and bpmp dicobalt(II) complexes were measured, [Fe2(Me4-tpdp)(RCO2)]2+ (RCO2 = C6H5CO2 and RCO2 = CF3CO2) and [Co2(L)(RCO2)]2+ (L = tpdp, RCO2 = CH3CO2, and L = bpmp, RCO2 = C6F5CO2, and CF3CO2), where Me4-tpdp, tpdp, and bpmp are N,N,N′,N′-tetrakis[(6-methyl-2-pyridyl)methyl]-1,3-diamino-2-propanolate, N,N,N′,N′-tetrakis(2-pyridylmethyl)-1,3-diamino-2-propanolate, and 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenolate, respectively. Within a series of the Ph-tidp diiron(II) complexes, dioxygen affinity is well correlated with electron donor ability of bridging carboxylates (1 (C6H5CO2) > 2 (C6F5CO2) > 3 (CF3CO2)). In contrast to the above trend, dioxygen affinities of the Ph-tidp complexes are lower than those of the Me4-tpdp complexes, although electron donor abilities of the Me4-tpdp complexes are weaker than those of the Ph-tidp complexes. Significant enhancement of dioxygen affinity was observed for both iron and cobalt complexes with 2,6-bis(aminomethyl)phenolate bridging skeleton compared to the complexes with a 1,3-diamino-2-propanolate bridging one. Thermodynamic study suggested that the observed enhancement is mainly attributable to a favorable entropy effect along with a steric effect.","subitem_description_type":"Abstract"}]},"item_4_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00010733","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.71.2267","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":"Sugimoto, Hideki"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Nagayama, Toshihiko"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Maruyama, Sachihito"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Fujinami, Shuhei"}],"nameIdentifiers":[{},{},{}]},{"creatorNames":[{"creatorName":"Yasuda, Yuichi"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"Suzuki, Masatatsu"}],"nameIdentifiers":[{},{},{}]},{"creatorNames":[{"creatorName":"Uehara, Akira"}],"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-SUGIMOTO-H-2267.pdf","filesize":[{"value":"2.1 MB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-SUGIMOTO-H-2267.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/10746/files/SC-PR-SUGIMOTO-H-2267.pdf"},"version_id":"db1b7548-091d-4ea3-a1c2-7ffb11b09455"}]},"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":"Thermodynamic Study on Dioxygen Binding of Diiron(II) and Dicobalt(II) Complexes Containing Various Dinucleating Ligands","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Thermodynamic Study on Dioxygen Binding of Diiron(II) and Dicobalt(II) Complexes Containing Various Dinucleating Ligands"}]},"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":"10746","relation_version_is_last":true,"title":["Thermodynamic Study on Dioxygen Binding of Diiron(II) and Dicobalt(II) Complexes Containing Various Dinucleating Ligands"],"weko_creator_id":"3","weko_shared_id":3},"updated":"2023-07-27T11:28:31.258620+00:00"}