{"created":"2023-07-27T06:50:18.150381+00:00","id":43029,"links":{},"metadata":{"_buckets":{"deposit":"c5dc8899-5466-48fa-a03e-9a48dd6ced12"},"_deposit":{"created_by":18,"id":"43029","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"43029"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00043029","sets":["2812:2813:2836"]},"author_link":["69217","3942"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1998-03","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"12p.","bibliographicVolumeNumber":"1995-1997","bibliographic_titles":[{"bibliographic_title":"平成9(1997)年度 科学研究費補助金 基盤研究(B) 研究成果報告書"},{"bibliographic_title":"1997 Fiscal Year Final Research Report","bibliographic_titleLang":"en"}]}]},"item_9_creator_33":{"attribute_name":"著者別表示","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{}],"nameIdentifiers":[{},{}]}]},"item_9_description_21":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"本研究では生体系で酸素運搬体として作用しているヘムエリトリンやヘモシアニン,酸素化触媒であるメタンモノオキシゲナーゼ(鉄および銅錯体)などの機能モデルとして,二核鉄及び銅酸素(μ-パーオキソ)錯体の設計・開発を行った。今年度は,二核鉄酸素錯体の熱的安定性と酸素親和性の制御および銅酸素錯体の単離と構造解析に重点を置き以下の成果が得られた。\n鉄錯体:1.様々な立体化学を有する二核化配位子を用い二核鉄パーオキソ錯体の不可逆的酸化に対する熱的安定性を検討した。その結果立体的にかさ高い置換基を配位基に導入することにより不可逆的酸化を大きく制御できることが明らかとなった。これは置換基の立体効果により配位子の電子供与性が弱められること,さらにそれらが酸素結合部位を立体的に保護するためであることがわかった。2.様々な二核鉄錯体の酸素化反応の熱力学パラメータを求めた。その結果,二核化配位子の架橋基の立体化学によって酸素親和性を数万倍の範囲で制御可能であることを見い出した。本研究で調べた一連の錯体の酸素親和性にはエルタルピー効果よりもエントロピーの効果が大きく寄与していることが明らかとなった。\n銅錯体:立体的にかさ高い様々な置換基を持つ三脚型四座配位子(8R_1R_2NCH_2CH_2)_3N : L)を用い銅(I)錯体([Cu(L)]^+)と酸素との反応性を調べた。その結果、-80℃の低温ではtrans-μ-1,2-peroxo 錯体が生成することが明らかとなった。また置換基にベンジル基を用いることにより単離可能となり,X線結晶構造解析からべンジル基が酸素結合部位を立体的に取り囲み酸素錯体を安定化していることがわかった。","subitem_description_type":"Abstract"},{"subitem_description":"Diiron-dioxygen and dicopper-dioxygen complexes play an important role in the reversible binding and activation of O_2 in biological and catalytic processes. We developed various diiron (II) and dicopper (I) complexes as functional models for O_2 transport proteins such as Hemerythrin (Fe_2) and hemocyanin (Cu_2) and mono-oxygenase such as methane monooxygenases (Fe_2 or Cu_n).\nDiiron Complexes : Only a few structurally and spectroscopically characterized diiron-dioxygen complexes have been reported. In order to synthesize the diiron-dioxygen complexes, it is important to control the ligand environment which is suitable for O_2 binding by two iron ions and stabilizes the mu-peroxo species toward irreversible oxidation. For this purpose, a series of dinucleating ligands with sterically hindered pyridyl and imidazolyl groups has been developed, which has an N_6O donor set with a phenolate or alkoxide bridging group. They form five-coordinate dinuclear [Fe_2 (L) (RCO_2)]^<2+> with an exoge nous carboxylate bridge, which react with O_2 to form mu-peroxo species. It was found that thermal stability toward irreversible oxidation and dioxygen affinity of those complexes are highly dependent on the stereochemistry and the electron donor ability of dinucleating ligands and bridging carboxylate. Finally we have succeeded in preparation and structural characterization of a cis-mu-1,2-peroxo diiron complex which is the first example of a crystallographically characterized diiron-dioxygen complex that binds O_2 reversibly at ambient temperature.\nDicopper Complexes : A series of copper (I) complexes ([Cu (L)]^+) having tripodal tetradentate ligands ((R_1R_2NCH_2CH_2)_3N : L) was synthesized. Reactivity of those complexes with O_2 was investigated. They form trans-mu-1,2-peroxo species at low temperature. It was found that stereochemistry and thermal stability of dioxygen complexes are highly dependent on the steric bulkiness of substituents (R). We have succeeded in structural characterization of a trans-mu-1,2-peroxo species ([Cu ((BnHNCH_2CH_2)_3N)]_2 (O_2)), where benzyl (Bn) groups form a cavity around Cu^<2+>-O_2^<2->-Cu^<2+> moiety, which stabilizes peroxo species.","subitem_description_type":"Abstract"}]},"item_9_description_22":{"attribute_name":"内容記述","attribute_value_mlt":[{"subitem_description":"研究課題/領域番号:07454175, 研究期間(年度):1995-1997","subitem_description_type":"Other"},{"subitem_description":"出典：「二核鉄,コバルト,銅酸素錯体の合成とその酸化・酸素化触媒能の研究」研究成果報告書　課題番号07454175\n(KAKEN：科学研究費助成事業データベース（国立情報学研究所）)\n　　　本文データは著者版報告書より作成","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00049378","subitem_identifier_reg_type":"JaLC"}]},"item_9_publisher_17":{"attribute_name":"公開者","attribute_value_mlt":[{"subitem_publisher":"金沢大学物質化学系"}]},"item_9_relation_28":{"attribute_name":"関連URI","attribute_value_mlt":[{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/search/?qm=20091390"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/search/?qm=20091390","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454175/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454175/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-07454175/074541751997kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-07454175/074541751997kenkyu_seika_hokoku_gaiyo/","subitem_relation_type_select":"URI"}}]},"item_9_version_type_25":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_ab4af688f83e57aa","subitem_version_type":"AM"}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2017-12-11"}],"displaytype":"detail","filename":"SC-PR-SUZUKI-M-kaken 1998-12p.pdf","filesize":[{"value":"503.8 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-SUZUKI-M-kaken 1998-12p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/43029/files/SC-PR-SUZUKI-M-kaken 1998-12p.pdf"},"version_id":"3f35ff19-28c0-440b-99d2-1181d2c6648f"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"jpn"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"research report","resourceuri":"http://purl.org/coar/resource_type/c_18ws"}]},"item_title":"二核鉄,コバルト,銅酸素錯体の合成とその酸化・酸素化触媒能の研究","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"二核鉄,コバルト,銅酸素錯体の合成とその酸化・酸素化触媒能の研究"},{"subitem_title":"Syntheses and Reactivity of Diiorn-, Dicobalt-, and Dicopper-Dioxygen Complexes","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2836"],"pubdate":{"attribute_name":"公開日","attribute_value":"2017-12-11"},"publish_date":"2017-12-11","publish_status":"0","recid":"43029","relation_version_is_last":true,"title":["二核鉄,コバルト,銅酸素錯体の合成とその酸化・酸素化触媒能の研究"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T14:49:58.822239+00:00"}