PREPARATION OF SYNERGETIC HYPERVALENT ELEMENT COMPOUNDS BASED ON THE CONTROL OF COORDINATION SPHERE

2009 Fiscal Year Final Research Report

• Project/Area Number: 18064013
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hiroshima University
• Principal Investigator: YAMAMOTO Yohsuke Hiroshima University, 大学院・理学研究科, 教授 (50158317)
• Project Period (FY): 2006 – 2009
• Keywords: 超原子価 / 5配位 / アンチモン / 異性化機構 / turnstile rotation / 理論計算

Research Abstract

1. We synthesized the first hypervalent hexacoordinate carbon compound (12-C-6) and the structure was confirmed by detailed X-ray analysis.
2. Synthetic methods for Cram's spehrand were improved and new derivatives bearing t-Bu and cyclohexyl substitutents were prepared in order to get more soluble compounds.
3. By use of the newly developed ligand, two stereoisomers of pentacoordinate antimony compounds (stiboranes) were synthesized, isolated, and characterized by X-ray analysis. Kinetic measurements were performed. Based on the calculation of the mechanism, we can conclude that the isomerization proceed by way of the turnstile rotation.

Research Products

• [Journal Article] Pentacoordinate Organoantimony Compounds that Isomerize by Turnstile Rotation (2009)
  • Author(s): Matsukawa, S.; Yamamich, H.; Yamamoto, Y.; Ando, K
  • Journal Title: J. Am. Chem. Soc 131(10) Pages: 3418-3419
  • Peer Reviewed
• [Journal Article] Reactions of [o-(Fluorodimethylsilyl)phenyl]lithium with GeCl2 and SnCl2: Preparation of Polyfunctionalized Four-Membered and Five-Membered Cyclic Linkages of Heavier Group 14 Elements (2009)
  • Author(s): Kawachi A.; Machida, K.; Yamamoto, Y
  • Journal Title: Organometallics 28(21) Pages: 6347-6351
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of a Hexacoordinate Carbon Compound (2008)
  • Author(s): Yamaguchi, T.; Yamamoto, Y.; Kinoshita, D.; Akiba, K-y.; Zhang, Y.; Reed, C.A.; Hashizume, D.; Iwasaki, F
  • Journal Title: J. Am. Chem. Soc 130(22) Pages: 6894-6895
  • Peer Reviewed
• [Journal Article] Synthesis of B/Si Bidentate Lewis Acids, o-(Fluorosilyl)(dimesitylboryl)benzenes, and Their Fluoride Ion Affinity (2008)
  • Author(s): Kawachi, A.; Tani, A.; Shimada, J.; Yamamoto, Y
  • Journal Title: J. Am. Chem. Soc 130(13) Pages: 4222-4223
  • Peer Reviewed
• [Journal Article] ynthesis, Structure, and Isomerization of Arylphosphoranes with Anti-apicophilic Bonding Modes Using a Novel Bidentate Ligand with Two C2F5 Groups (2008)
  • Author(s): Jiang, X.; Matsukawa, S,; Yamamoto, Y
  • Journal Title: Dalton Trans Pages: 3678-3687
  • Peer Reviewed
• [Journal Article] Synthesis and Application of a Bidentate Ligand Based on Decafluoro-3-phenyl-3-pentanol: Steric Effect of Pentafluoroethyl Groups on the Stereomutation of O-Equatorial C-Apical Spirophosphoranes (2007)
  • Author(s): Jiang, X.; Kakuda, K.; Matsukawa, S.; Yamamich, H.; Kojima, S.; Yamamoto, Y
  • Journal Title: Chem. Asian J 2 Pages: 314-323
  • Peer Reviewed
• [Journal Article] Syntheses, Crystal and Solution Structures, Ligand Exchange, and Ligand Coupling Reactions of Mixed Pentaarylantimony Compounds, Schroeder (2007)
  • Author(s): G.; Okinaka, T.; Mimura, Y.; Watanabe, M.; Matsuzaki, T.; Hasuoka, A.; Yamamoto, Y.; Matsukawa, S.; Akiba, K-y
  • Journal Title: Chem. -Eur. J 13(9) Pages: 2517-2529
  • Peer Reviewed
• [Journal Article] First Isolation and Kinetic Study of Hypervalent 10-As-5 Organoarsenic Compounds with a C-Apical O-Equatorial Configuration (2007)
  • Author(s): Jiang, X.; Matsukawa, S.; Yamamich, H; Yamamoto, Y
  • Journal Title: Inorg. Chem 46(14) Pages: 5480-5482
  • Peer Reviewed
• [Journal Article] Experimental Determination of nN→σ*P-O Interaction Energy of O-Equatorial C-Apical Phosphoranes Bearing a Primary Amino Group (2006)
  • Author(s): Adachi, T.; Matsukawa, S.; Nakamoto, M.; Kajiyama, S.; Kojima, S.; Yamamoto, Y.; Akiba, K. -y.; Re, S.; Nagase, S
  • Journal Title: Inorg. Chem 45 Pages: 7269-7277
  • Peer Reviewed
• [Presentation] Synthesis and Structire of Hypervalent Penta- and Hexacoordinate Carbon and Boron Compounds (2009)
  • Author(s): Y. Yamamoto
  • Organizer: Symposium on Creation of Functional Materials
  • Place of Presentation: Tsukuba, Japan
  • Year and Date: 2009-12-13
• [Presentation] 偶然の発見:非芳香族性16πポルフィリンの合成とその後の展開 (2009)
  • Author(s): 山本陽介
  • Organizer: 第25回若手研究者のための化学道場
  • Place of Presentation: 松山
  • Year and Date: 2009-09-07
• [Presentation] 新規16πポルフィリンの合成と金属化合物との反応 (2008)
  • Author(s): 山本陽介
  • Organizer: 近畿化学協会有機金属部会平成20年度第3回例会
  • Place of Presentation: 仙台
  • Year and Date: 2008-10-30
• [Presentation] Synthesis of 5-Coordinate and 6-Coordinate Hypervalent Carbon and Boron Compounds and Recent Developments (2008)
  • Author(s): Y. Yamamoto, T. Yamaguchi, K-y. Akiba, C.A. Reed, D. Hashizume, F. Iwasaki
  • Organizer: The 3rd BK21 International Symposium
  • Place of Presentation: Busan, Korea
  • Year and Date: 2008-10-13
• [Presentation] 超原子価有機典型元素の合成とその展開 (2007)
  • Author(s): 山本陽介, 山口虎彦
  • Organizer: 理学研究流動機構シンポジウム「元素の個性～どう見るか, どうつくるか, どう使うか～」
  • Place of Presentation: 東京
  • Year and Date: 2007-11-30
• [Presentation] Synthesis of Hypervalent Pentacoordinate and Hexacoordinate Carbon Compounds (2007)
  • Author(s): shita, K-y. Akiba, C.A. Reed, D. Hashizume, F. Iwasaki
  • Organizer: 8th International Conference on Heteroatom Chemistry(ICHAC-8) Riverside
  • Place of Presentation: U.S. A
  • Year and Date: 2007-08-13
• [Presentation] Synthesis and Structure of Hypervalent Pentacoordinated Boron Compounds (2006)
  • Author(s): Y. Yamamoto
  • Organizer: The 232nd ACS National Meeting, Exposition
  • Place of Presentation: San Francisco, U.S. A
  • Year and Date: 2006-09-13
• [Presentation]
  • Author(s): http://home.hiroshima-u.ac.jp/hetero/top.html