{"created":"2023-07-27T06:57:10.129798+00:00","id":54238,"links":{},"metadata":{"_buckets":{"deposit":"f05152fd-2c9a-493f-9e26-38906659c429"},"_deposit":{"created_by":18,"id":"54238","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"54238"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00054238","sets":["2812:2813:2828"]},"author_link":["54"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2018-03-28","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"2p.","bibliographicVolumeNumber":"2004 – 2005","bibliographic_titles":[{"bibliographic_title":"平成17(2005)年度 科学研究費補助金 特定領域研究 研究概要"},{"bibliographic_title":"2005 Research Project Summary","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,生体系での酸素活性化金属タンパクや合成化学的に重要な酸化触媒の機能発現機i構の解明を目的として,三脚型4座配位子(Me_2-tpa=tris(6-methyl-2-pyridylmethyl)amine)を含むbis(μ-hydroxo)dinickel(II)錯体([Ni_2(OH)_2(Me_2-tpa)_2]^<2+>(1))と過酸化水素との反応により配位子に組み込んだ6-メチル基がカルボン酸およびアルコールへと酸化される動的過程を調べた。低温での反応により酸素活性種を含む一連の反応中間体の単離,構造解析及び反応性の研究に成功し以下の結果が明らかとなった。すなわち錯体1と過酸化水素との反応でbis(μ-oxo)dinickel(III)錯体([Ni_2(O)_2(Me_2-tpa)_2]^<2+>(2))が生成する。この錯体2は,配位子Me_2-tpaの6-メチル基の水素原子を引抜きラジカル(Me-tpa-CH_2・)を生成し,このラジカルは酸素分子と反応して配位子のペルオキシルラジカル(Me-tpa-CH_2OO・)を生成する。このペルオキシラジカルは,錯体2と過酸化水素との反応で生成したbis(μ-superoxo)dinickel(II)錯体([Ni_2(O_2)_2(Me_2-tpa)_2]^<2+>(3))と反応して,(μ-hydroxo)(μ-alkylperoxo)dinickel(II)錯体([Ni_2(OH)(Me_2-tpa)-(Me-tpa-CH_2OO^-]^<2+>)を生成する。このペルオキソ基(Me-tpa-CH_2OO^-)の酸素-酸素開裂により配位子のアルデヒド(Me-tpa-CHO)が生成し,Cannizzaro反応によるアルデヒドの不均化反応によりカルボン酸とアルコールが生成することが明らかとなった(Inorg.Chem. in press)。","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:16033222, 研究期間(年度):2004-2005","subitem_description_type":"Other"},{"subitem_description":"出典：「金属錯体による酸素: 酸素結合の開裂と生成の動的制御」研究成果報告書　課題番号16033222\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（https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-16033222/)を加工して作成","subitem_description_type":"Other"}]},"item_9_description_5":{"attribute_name":"提供者所属","attribute_value_mlt":[{"subitem_description":"金沢大学理工研究域","subitem_description_type":"Other"}]},"item_9_identifier_registration":{"attribute_name":"ID登録","attribute_value_mlt":[{"subitem_identifier_reg_text":"10.24517/00060514","subitem_identifier_reg_type":"JaLC"}]},"item_9_relation_28":{"attribute_name":"関連URI","attribute_value_mlt":[{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/search/?kw=20091390"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/search/?kw=20091390","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-16033222/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/ja/grant/KAKENHI-PROJECT-16033222/","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":"2021-06-11"}],"displaytype":"detail","filename":"SC-PR-SUZUKI-M-kaken 2018-2p.pdf","filesize":[{"value":"134.7 kB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-SUZUKI-M-kaken 2018-2p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/54238/files/SC-PR-SUZUKI-M-kaken 2018-2p.pdf"},"version_id":"441acb7f-f723-446f-8e0b-3ce751f678c1"}]},"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":"金属錯体による酸素: 酸素結合の開裂と生成の動的制御","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"金属錯体による酸素: 酸素結合の開裂と生成の動的制御"}]},"item_type_id":"9","owner":"18","path":["2828"],"pubdate":{"attribute_name":"公開日","attribute_value":"2021-06-11"},"publish_date":"2021-06-11","publish_status":"0","recid":"54238","relation_version_is_last":true,"title":["金属錯体による酸素: 酸素結合の開裂と生成の動的制御"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T14:30:09.341160+00:00"}