Relationship between electronic structure and reactivity of various high-valent metal complexes

• Project/Area Number: 22550055
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Ibaraki University
• Principal Investigator: SHIMAZAKI Yuichi 茨城大学, 理学部, 准教授 (80335992)
• Project Period (FY): 2010 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2012: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2011: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2010: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
• Keywords: 酸化 / 還元反応 / 酸化数 / 10属金属イオン / 銅イオン / フェノキシルラジカル / 無機化学 / 酸化・還元反応 / 金属イオン

Research Abstract

A series of one-electron oxidized metal(II) salen-type complexes were prepared allowing for a comparison of the electronic structure between 5- and 6-membered chelate backbone. The chelate ring-size difference of the diamine backbone gave different electronic structure of the oxidized Cu(II) complex, the 5-membered chelate complex was assigned to a Cu(III) ground state, while the 6-membered chelate complex was a Cu(II)-phenoxyl radical. Investigation of the reactivity of these oxidized complex revealed that reaction rate of the Cu(II)-phenoxyl radical was fastest in the series of oxidized species.

Research Products

• [Journal Article] Double oxidation localizes spin in a Ni bis-phenoxyl radical complex (2013)
  • Author(s): Tim J. Dunn, Michael I. Webb, Khatera Hazin, Pratik Verma, Erik C. Wasinger, Yuichi Shimazaki and Tim Storr
  • Journal Title: Dalton Trans. Volume: 42 Issue: 11 Pages: 3950-3956
  • DOI: 10.1039/c2dt32632a
  • Peer Reviewed
• [Journal Article] Radical localization in a series of symmetric Ni^<II> complexes with oxidized salen ligands (2013)
  • Author(s): Linus Chiang, Amelie Kochem, Olivier Jarjayes, Tim J. Dunn, Herve Vezin, Miyuki Sakaguchi, Takashi Ogura, Maylis Orio, Yuichi Shimazaki, Fabrice Thomas and Tim Storr
  • Journal Title: Chemistry-A European Journal Volume: 18 Issue: 44 Pages: 14117-14127
  • DOI: 10.1002/chem.201201410
  • Peer Reviewed
• [Journal Article] (2012)
  • Author(s): K. Asami, K. Tsukidate, S. Iwatsuki, F. Tani, S. Karasawa, L. Chiang, T. Storr, F. Thomas, Y. Shimazaki
  • Journal Title: Inorg. Chem Volume: 51 Issue: 22 Pages: 12450-12450
  • DOI: 10.1021/ic3018503
  • Peer Reviewed
• [Journal Article] (2012)
  • Author(s): L. Chiang, A. Kochem, O. Jarjayes, T. J. Dunn, H. Vezin, M. Sakaguchi, T. Ogura, M. Orio, Y. Shimazaki, F. Thomas T. Storr
  • Journal Title: Chem. Eur. J Volume: 18 Issue: 35 Pages: 14117-14117
  • DOI: 10.1002/chem.201103450
• [Journal Article] (2012)
  • Author(s): Y. Shimazaki, O. Yamauchi
  • Journal Title: Chemistry & Biodiversity (Review) Volume: 9 Issue: 9 Pages: 1635-1635
  • DOI: 10.1002/cbdv.201100446
• [Journal Article] (2012)
  • Author(s): A. Kochem, O. Jarjayes, B. Baptiste, C. Philouze, H. Vezin, K. Tsukidate, F. Tani, M. Orio, Y. Shimazaki, F. Thomas
  • Journal Title: Chem. Eur. J Volume: 18 Issue: 4 Pages: 1068-1068
  • DOI: 10.1002/chem.201102882
  • Peer Reviewed
• [Journal Article] Non-innocent ligand behaviour of a bimetallic Cu complex employing a bridging catecholate (2012)
  • Author(s): Tim J. Dunn, Linus Chiang, Caterina F. Ramogida, Mike I. Webb, Didier Savard, Miyuki Sakaguchi, Takashi Ogura, Yuichi Shimazaki and Tim Storr
  • Journal Title: Dalton Transactions Volume: 41 Issue: 26 Pages: 7905-7914
  • DOI: 10.1039/c2dt30444a
  • Peer Reviewed
• [Journal Article] Synthesis and properties of charge-transfer solids with cluster units [Mo6X14]2－ (X = Br, I) (2012)
  • Author(s): Gunzi Saito, et.al.
  • Journal Title: J. Mater. Chem. Volume: 22 Issue: 37 Pages: 19774-19791
  • DOI: 10.1039/c2jm33086e
  • Peer Reviewed
• [Journal Article] Synthesis, Characterization, and Small Hydrocarbon Encapsulation of Dicavitand-Porphyrins (2012)
  • Author(s): J. Nakazawa, J. Hagiwara, Y. Shimazaki, F. Tani, Y. Naruta
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 85 Issue: 8 Pages: 912-919
  • DOI: 10.1246/bcsj.20120107
  • NAID: 130004153093
  • Peer Reviewed
• [Journal Article] Supramolecular Structures of Inclusion Complexes of Cyclic Porphyrin Dimers and PCBM [6,6]-Phenyl-C_<61>-Butyric Acid Methyl Ester (2012)
  • Author(s): H. Nobukuni, T. Kamimura, H. Uno, Y. Shimazaki, Y. Naruta, F. Tani
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 85 Issue: 8 Pages: 862-868
  • DOI: 10.1246/bcsj.20120073
  • NAID: 130004153091
  • Peer Reviewed
• [Journal Article] (2011)
  • Author(s): T. J. Dunn, C. F. Ramogida, C. Simmonds, A. Paterson, E. W. Y. Wong, L. Chiang, Y. Shimazaki, T. Storr
  • Journal Title: Inorg. Chem Volume: 50 Issue: 14 Pages: 6746-6746
  • DOI: 10.1021/ic200785g
  • Peer Reviewed
• [Journal Article] Influence of the chelate effect on the electronic structure of one-electron oxidized group 10 metal(II)-(disalicylidene) diamine complexes (2011)
  • Author(s): Y.Shimazaki, et.al.
  • Journal Title: Dalton Trans. Volume: 40 Issue: 11 Pages: 2469-2479
  • DOI: 10.1039/c0dt01574a
  • Peer Reviewed
• [Journal Article] (2011)
  • Author(s): Y. Shimazaki, O. Yamauchi
  • Journal Title: Ind. J. Chem. A, (Review) Volume: 50A Pages: 383-383
  • URL: http://nopr.niscair.res.in/bitstream/123456789/11231/1/IJCA
• [Journal Article] Recent advances in metal-phenoxyl radical chemistry (2011)
  • Author(s): Y.Shimazaki, O.Yamauchi
  • Journal Title: Indian.J.Chem.A Volume: 50 Pages: 383-394
  • Peer Reviewed
• [Journal Article] Concentration-Dependent Palladium(II)-Indole Bond Formation in Complexes with a 2N-Donor Ligand Containing an Indole Moiety (2011)
  • Author(s): S. Iwatsuki, T. Suzuki, T. Yajima, T. Shiraiwa, O. Yamauchi, Y. Shimazaki
  • Journal Title: Synthesis, Characterization, and Reaction Analysis, Inorg. Chim. Acta Volume: 377 Issue: 1 Pages: 111-119
  • DOI: 10.1016/j.ica.2011.07.045
  • Peer Reviewed
• [Journal Article] Supramolecular Structures of Inclusion Complexes of C_<70> and Cyclic Porphyrin Dimers (2011)
  • Author(s): H. Nobukuni, T. Kamimura, H. Uno, Y. Shimazaki, Y. Naruta, F. Tani
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 84 Issue: 12 Pages: 1321-1328
  • DOI: 10.1246/bcsj.20110248
  • NAID: 130004152845
  • Peer Reviewed
• [Journal Article] Influence of the chelate effct on the electronic structure ofone-electron oxidized group 10 metal(II)-(disalicylidene)diamine complexes (2011)
  • Author(s): Y.Shimazaki, N.Arai, T.J.Dunn, T.Yajima, F.Tani, C.F.Ramogida, T.Storr
  • Journal Title: Dalton Trans. Volume: In press(未定)
  • Peer Reviewed
• [Journal Article] Recent advances in metal-phenoxyl radical chemistry (2011)
  • Author(s): Y.Shimazaki, O.Yamauchi
  • Journal Title: Ind.J.Chem.A. Volume: In press(未定)
  • Peer Reviewed
• [Journal Article] (2010)
  • Author(s): T. Storr, P. Verma, Y. Shimazaki, E. C. Wasinger, T. D. P. Stack
  • Journal Title: Chem. Eur. J Volume: 16 Issue: 30 Pages: 8980-8980
  • DOI: 10.1002/chem.201001401
• [Journal Article] Unprecedented formation of binuclear copper(II)complex with a perylene derived ligand by the oxidative reaction (2010)
  • Author(s): J.Hagiwara, Y.Shimazaki, G.Saito
  • Journal Title: Inorg.Chim.Acta Volume: 363 Pages: 3178-3185
  • NAID: 120002770947
  • Peer Reviewed
• [Journal Article] Ligand Radical Localization in a Nonsymmetric One-Electron Oxidized Nill Bis-phenoxide Complex (2010)
  • Author(s): T.Storr, P.Verma, Y Shimazaki, E.C.Wasinger, T.D.P.Stack
  • Journal Title: Chem.Eur.J. Volume: 16 Pages: 8980-8983
  • Peer Reviewed
• [Journal Article] Supramolecular Structures and Photoelectronic Properties of the inclusion Complex of a Cyclic Free-Base Porphyrin Dimer and C_60 (2010)
  • Author(s): H.Nobukuni, Y.Shimazaki, H.Uno, Y.Naruta, K.Ohkubo, T.Kojima, S.Fukuzumi, S.Seki, H.Sakai, T.Hasobe, F.Tani
  • Journal Title: Chem.Eur.J. Volume: 16 Pages: 11611-11623
  • Peer Reviewed
• [Presentation] Characterization and reactivity of one-electron oxidized copper(II)-salen-type complexes (2013)
  • Author(s): Yuichi Shimazaki
  • Organizer: Zing conference Bioinorganic Chemistry Conference
  • Place of Presentation: Lanzarote, Spain
  • Invited
• [Presentation] 銅(II)-salen 錯体の一電子酸化体の電子状態と反応性 (2013)
  • Author(s): 島崎優一
  • Organizer: 東北大学卓越大学院研究会
  • Place of Presentation: 東北大学 仙台市
  • Invited
• [Presentation] 各種銅（II）-salenの一電子酸 化体の電子状態と反応性の相関 (2012)
  • Author(s): 島崎優一
  • Organizer: 中部化学関係学協会連合協議会
  • Place of Presentation: 名古屋工業大学 名古屋市
  • Invited
• [Presentation] Characterization and Reactivity of one-electron oxidized Cu(II)-salen-type complexes (2012)
  • Author(s): Kazutaka, Asami, Kazuaki Tsukidate, Yuichi Shimazaki
  • Organizer: 12th European Biological Inorganic Chemistry Conference (EUROBIC 12)
  • Place of Presentation: GRANADA, SPAIN
• [Presentation] Electronic Structures and Reactivities of Oxidized Metal(II)-salen-type Complexes (2012)
  • Author(s): Yuichi Shimazaki
  • Organizer: Challenges in Inorganic and Materials Chemistry (ISACS8)
  • Place of Presentation: Tronto, Canada
• [Presentation] Electronic Structures of Oxidized Metal(II)-salen Type Complexes Dependence with the Diamine Backbone (2011)
  • Author(s): Yuichi Shimazaki
  • Organizer: The 15th International Conference on Biological Inorganic Chemistry University of British Colombia
  • Place of Presentation: Vancouver, Canada
• [Presentation] Influence of the Chelate Effect on the Electronic Structure of Oxidized Metal(II)-(disalicylidene)diamine Complexes (2011)
  • Author(s): Yuichi Shimazaki
  • Organizer: First EuCheMS Inorganic Chemistry Conference University of Manchester
  • Place of Presentation: UK
• [Presentation] Influence of the Chelate Effect on the Electronic Structure of Oxidized Metal(II)-(disalicylidene)diamine Complexes (2011)
  • Author(s): Y.Shimazaki
  • Organizer: First EuCheMS Inorganic Chemistry Conference
  • Place of Presentation: University of Manchester, UK
• [Presentation] Concentration-dependent Pd(II)-C bond formation in complexes with a 2N-donor ligand containing an indole moiety (2011)
  • Author(s): T.Suzuki, S.Iwatsuki, Y.Shimazaki
  • Organizer: 18th International SPACC Symposium
  • Place of Presentation: Whistler, Canada(招待講演)
• [Presentation] Electronic Structures of Oxidized Metal(II)-salen Type Complexes Dependence with the Diamine Backbone (2011)
  • Author(s): Y.Shimazaki
  • Organizer: The 15th International Conference on Biological Inorganic Chemistry
  • Place of Presentation: University of British Colombia, Vancouver, Canada(招待講演)
• [Presentation] Pd(II)-C bond formation mechanism in various Pd complexes containing an indole moiety (2011)
  • Author(s): Y.Shimazaki, T.Suzuki, S.Iwatsuki, T.Yajima
  • Organizer: 5th EuCheMS Conference on NITROGEN LIGANDS
  • Place of Presentation: Granada, Spain
• [Presentation] Concentration-dependent Pd(II)-C bond formation in complexes containing an indole moiety (2011)
  • Author(s): Y.Shimazaki, S.Iwatsuki
  • Organizer: International Symposium on Applied Bioinorganic Chemistry
  • Place of Presentation: Barcelona, Spain
• [Presentation] Characterizations and electronic structures of oxidized metal(II)-salen-type complexes (2010)
  • Author(s): Yuichi Shimazaki
  • Organizer: PACIFICHEM 2010
  • Place of Presentation: Honolulu, Hawaii, USA
• [Presentation] 金属(II)salen錯体の一電子酸化体の電子構造 (2010)
  • Author(s): 島崎優一
  • Organizer: 第4回日本化学会関東支部大会
  • Place of Presentation: 筑波大学
• [Presentation] Characterization of One-Electron Oxidized Metal-Salen Type Complexes (Metal = Cu, Ni, Pd, Pt (2010)
  • Author(s): Yuichi Shimazaki
  • Organizer: The 39^<th> International Conference on Coordination Chemistry (ICCC 39)
  • Place of Presentation: Adelaide, Australia
• [Presentation] Electronic Structures and Reactivities of Oxidized Metal(II)-salen type Complexes (2010)
  • Author(s): Yuichi Shimazaki
  • Organizer: Faraday Discussion 148: Spectroscopy, Theory and Mechanism in Bioinorganic Chemistry
  • Place of Presentation: University of Nottingham, UK
• [Presentation] Synthesis and characterization of Pd-indole complexes (2010)
  • Author(s): Y.Shimazaki
  • Organizer: 10^<th>european biological inorganic chemistry conference(EUROBIC 10)
  • Place of Presentation: ギリシャテサロニキ
• [Presentation] Characterization of one-electron oxidized metal-salen type complexes(metal=Cu, Ni, Pd, Pt) (2010)
  • Author(s): Y.Shimazaki
  • Organizer: 39^<th> international conference on coordination themistry(ICCC 39)
  • Place of Presentation: オーストラリア アデレード
• [Presentation] 金属(II)salen錯体の一電子酸化体の電子構造 (2010)
  • Author(s): 島崎優一
  • Organizer: 第4回日本化学会関東支部大会
  • Place of Presentation: 筑波大学つくば市
• [Presentation] Characterizations and electronic structures of oxidized metal-salen type complexes (2010)
  • Author(s): Y Shimazaki
  • Organizer: 2010環太平洋国際化学会議2010(Pacifichem 2010)
  • Place of Presentation: アメリカ合衆国ホノルル
• [Book] Electrochemistry (2013)
  • Author(s): Yuichi Shimazaki
  • Publisher: Ed. M. A. A. Khalid
• [Book] The chemistry of metal-phenolate (2013)
  • Author(s): Yuichi Shimazaki
  • Publisher: Ed. J. Zabicky
• [Book] The Chemistry of Metal-Phenolates (2013)
  • Author(s): Yuichi Shimazaki
  • Publisher: John Wiley & Sons
• [Book] Electrochemistry (2013)
  • Author(s): Yuichi Shimazaki
  • Total Pages: 198
  • Publisher: INTECH
• [Book] ベーシックマスター 無機化学(増田秀樹・長嶋雲兵 共編) (2010)
  • Author(s): 島崎優一
  • Publisher: オーム社