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

2012 Fiscal Year Final Research Report

• 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
• 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

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] (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 Pages: 12450
  • DOI: doi:10.1021/ic3018503
• [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 Pages: 14117
  • DOI: doi:10.1002/chem. 201103450
• [Journal Article] (2012)
  • Author(s): Y. Shimazaki, O. Yamauchi
  • Journal Title: Chemistry & Biodiversity (Review) Volume: 9 Pages: 1635
  • DOI: 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 Pages: 1068
  • DOI: doi:10.1002/chem.201102882
• [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 Pages: 6746
  • DOI: doi:10.1021/ic200785g
• [Journal Article] (2011)
  • Author(s): Y. Shimazaki, N. Arai, T. J. Dunn, T. Yajima, F. Tani, C. F. Ramogida, T. Storr
  • Journal Title: Dalton Trans Volume: 40 Pages: 2469
  • DOI: doi:10.1039/C0DT01574A
• [Journal Article] (2011)
  • Author(s): Y. Shimazaki, O. Yamauchi
  • Journal Title: Ind. J. Chem. A, (Review) Volume: 50A Pages: 383
  • URL: http://nopr.niscair.res.in/bitstream/123456789/11231/1/IJCA
• [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 Pages: 8980
  • DOI: doi:10.1002/chem.201001401
• [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
  • Year and Date: 20110807-12
• [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
  • Year and Date: 20110411-14
• [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
  • Year and Date: 20101215-20
• [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
  • Year and Date: 20100829-30
• [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
  • Year and Date: 20100725-30
• [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
  • Year and Date: 20100705-07
• [Book] Electrochemistry (2013)
  • Author(s): Yuichi Shimazaki
  • Total Pages: 51-70
  • Publisher: Ed. M. A. A. Khalid
• [Book] The chemistry of metal-phenolate (2013)
  • Author(s): Yuichi Shimazaki
  • Publisher: Ed. J. Zabicky