{"created":"2023-07-27T06:50:18.015109+00:00","id":43026,"links":{},"metadata":{"_buckets":{"deposit":"f33350c8-9e28-4dbd-aa98-f594078bcc91"},"_deposit":{"created_by":18,"id":"43026","owners":[18],"pid":{"revision_id":0,"type":"depid","value":"43026"},"status":"published"},"_oai":{"id":"oai:kanazawa-u.repo.nii.ac.jp:00043026","sets":["2812:2813:2827"]},"author_link":["69217","3942"],"item_9_biblio_info_8":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2007-03","bibliographicIssueDateType":"Issued"},"bibliographicPageStart":"14p.","bibliographicVolumeNumber":"2004-2006","bibliographic_titles":[{"bibliographic_title":"平成18(2006)年度 科学研究費補助金 基盤研究(B) 研究成果報告書"},{"bibliographic_title":"2006 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":"生体系には,酸素運搬能を有するHemocyanin(Hc)や,チロシンのフェノールを水酸化するTyrosinase(Tyr)などがある。いずれも二核銅中心を持ち酸素分子と反応して(μ-η^2:η^2-peroxo)二核銅(II)錯体を生成するが,その機能は全く異なっている。また,メタンをメタノールに酸化するParticulate methane monooxygenase(pMMO)の反応中間体でも二核銅-酸素錯体の可能性が示唆されているが,現在のところ詳細は不明である。本研究では,このような銅酵素で見出されている活性中間体を小分子で再現し,その反応性を調べることを目的とした。\n二核化配位子1,3-bis[bis(6-methyl-2-pyridylmethyl)aminomethyl]benzene(L)を含む二核銅(I)錯体は,-80℃の低温で酸素分子と反応して(μ-η^2:η^2-peroxo)二核銅(II)錯体を生成する。このペルオキソ錯体は,低温でも反応性に富み配位子に組込んだキシリル基を親電子的置換反応で水酸化し,Tyrと類似の反応性を有している。本錯体のDFT計算により推定される構造から,ペルオキソ基への外部基質の接近が可能であることが分かった。そこで,本錯体と様々なC-H結合解離エネルギー(75-89kcal mol^<-1>)を持つ脂肪族化合物との反応性を調べた。その結果,ペルオキソ基は水素原子引き抜き能を持つことが分かった。速度論的研究により,この水素原子引抜き反応はラジカル的反応であることを明らかにし,pMMOと同様にC-H結合を活性化する能力を持つことが明らかとなった。さらに,本錯体のペルオキソ基の反応性をクミルペルオキシドラジカルと比較検討した結果,これら両者は非常に良く似た反応性を持つことが明らかとなった。","subitem_description_type":"Abstract"},{"subitem_description":"The purpose of this project is the development of the peroxo-dicopper(II) and diiron(III) complexes as functional models for tyrosinase and toluene monooxygenase.\nWe have succeeded in synthesis of (μη^2:η^2-peroxo)Cu(II)_2 complexes, [Cu_2(O_2)(R-L)]^<2+> (oxy-R-1: R = H, MeO, t-Bu, and NO_2), where R-L = 1,3-Bis[bis(6-methyl-2pyridylmethyl)aminomethy1]-5-R-benzene, which can perform not only hydroxylation of the m-xylyl linker of R-L, but also epoxidation of styrene via an electrophilic addition of the peroxide to the C=C bond, the latter of which is the first example of the epoxidation of styrene by a discrete (μη^2:η^2-peroxo)Cu(II)_2 species. In addition, oxy-H-1 can oxidize various aliphatic C-H bonds via H-atom abstraction. A linear correlation between log k (the second order rate constants of oxidation) and the bond dissociation energies of the C-H bonds was observed. The results provide new insights into the reactivity of (μη^2:η^2 peroxo) Cu(II)_2 complexes.\n(μ-Peroxo)diiron(III) Complex: A Functional Model for Toluene Monooxygenase. We have succeeded in synthesis of two types of peroxodiiron(III) complexes, [Fe2(L^<Ph4>)(RCO_2)(O_2)]^<2+> (R = Ph_3C (oxy-1) and Ph (oxy-2)), the former leads to regioselective hydroxylation of a phenyl group of L^<Ph4> and the latter exhibits reversible deoxygenation (L^<Ph4> = N, N, N',N'-tetrakis[(1-methyl-2-pheny1-4-imidazolyl)methy1]-1,3-diamino-2-propanolate). This is the first example of the peroxodiiron(III) complex which is capable of arene hydroxylation. The reactions mimic toluene monooxygenase and hemerythrin reactivity, respectively. They provide new insights into the reactivity of the peroxodiiron(III) complexes having a nitrogen-rich coordination environment like alkane arhydroxylase and hemerythrin.","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:16350030, 研究期間(年度):2004-2006","subitem_description_type":"Other"},{"subitem_description":"出典：「酸素活性種を含む金属錯体の創製と機能制御」研究成果報告書　課題番号16350030\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":"10.24517/00049375","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-16350030/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-16350030/","subitem_relation_type_select":"URI"}},{"subitem_relation_name":[{"subitem_relation_name_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-16350030/163500302006kenkyu_seika_hokoku_gaiyo/"}],"subitem_relation_type_id":{"subitem_relation_type_id_text":"https://kaken.nii.ac.jp/report/KAKENHI-PROJECT-16350030/163500302006kenkyu_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 2007-14p.pdf","filesize":[{"value":"2.6 MB"}],"format":"application/pdf","licensetype":"license_11","mimetype":"application/pdf","url":{"label":"SC-PR-SUZUKI-M-kaken 2007-14p.pdf","url":"https://kanazawa-u.repo.nii.ac.jp/record/43026/files/SC-PR-SUZUKI-M-kaken 2007-14p.pdf"},"version_id":"910d8857-6ac0-476b-a398-3907de61d71f"}]},"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":"酸素活性種を含む金属錯体の創製と機能制御","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"酸素活性種を含む金属錯体の創製と機能制御"},{"subitem_title":"Synthesis and Control of Functions of Metal Complexes Having Oxygen Active Species","subitem_title_language":"en"}]},"item_type_id":"9","owner":"18","path":["2827"],"pubdate":{"attribute_name":"公開日","attribute_value":"2017-12-11"},"publish_date":"2017-12-11","publish_status":"0","recid":"43026","relation_version_is_last":true,"title":["酸素活性種を含む金属錯体の創製と機能制御"],"weko_creator_id":"18","weko_shared_id":-1},"updated":"2023-07-27T14:34:32.624398+00:00"}