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The structure and the catalytic activity of diphenylboron cation in solution

Research Project

Project/Area Number 17550039
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKyushu University :

Principal Investigator

FUJIO Mizue  Kyushu Univ., Researcher Inst.for Materials Chem.and Eng., Researcher, 先導物質化学研究所, 研究員 (10029887)

Project Period (FY) 2005 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2005: ¥2,300,000 (Direct Cost: ¥2,300,000)
KeywordsBoron Cation / B-11 NMR Chemical Shift / Lewis Acidity / ab initio Calculation / Lewis Acid Catalyst / B-11 NMR化学シフト
Research Abstract

A novel boron cationic behavior of diphenylchloroborane has been investigated by utilyzing the Lewis acids in aprotic solvents at room temperature, by monitoring ^<11>B, ^<13>C, and ^<121>Sb NMR spectroscopy in-situ, and the cationic species was confirmed by a correlation between the calculated and the experimental ^<11>B NMR chemical shifts. The heterolysis of diphenylchloroborane by the strong Lewis acid (SbCI_5, GaCI_3, AIBr_3) in nitromethane gave the nitromethane solvated diphenylboronium ion stabilized by electron donating O-atom of two nitromethane molecules. The nitromethane coordinated complex-ion can be converted into MeCN or THF coordinated complex-ion by adding 2 equivalents of solvents, and finally to the pyridine complex-ion. These four-coordinate diphenylboronium ions have no Lewis acidity due to coordination of nucleophiles. The abstraction of chloride ion from diphenylchloroborane did not proceed in non- nucleophilic solvents nor with AICI_3 and BCl_3 even in nitrometh … More ane. Treatment of diphenylchloroborane with one equivalent of pyridine in dichloromethane afforded the corresponding 1:1 adduct that gave highly Lewis acidic tricoordinate diphenylborenium ion by abstraction of chloride ion with the strong Lewis acid. The tricoordinate diphenylborenium ion existed in an equilibrium with the nitrometane-coordinate sp^3 cation in nitromethane depending on the substituent in pyridine while that in dichloromethane exists solely as sp^2 diphenylborenium ion for 4-NMe_2 to H substituent. The experimental ^<11>B chemical shifts of all species were in good agreement with the ab initio calculation results at the level of GIAO-HF/6-311+G(2d, p)//B3LYP/6-31+G(d), and the optimized structures were compatible with the ^<11>B, ^<13>C and ^<121>Sb NMR spectroscopy. In conclusion, the sp diphenylborinium ion ([Ph_2B]^+) incipiently produced was stablized by the π back-bonding (B-O or B-N) from solvent(s) and/or pyridine(s) to positive boron atom and these boron cation species should have an appreciably long life to exist as sp^2([Ph_2B(Py)]^+) or sp^3 diphenylboron cation ([Ph_2B(Py)NO_2Me]^+, [Ph_2B(PY)_2]^+), and [Ph_2B(Solv)_2]^+). Less

Report

(3 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report

Research Products

(17 results)

All 2007 2006 2005

All Journal Article (17 results)

  • [Journal Article] Aminolysis of Y-Substituted Phenyl X-Substituted Cinnamates and Benzoates : Effect of Modification of Nonleaving Group from Benzoyl to Cinnamoyl2007

    • Author(s)
      I.-H.Um et al.
    • Journal Title

      J. Org. Chem. 72 (in press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] ジメチルアニリニウムイオン系の気相酸性度に及ぼす置換基効果に関する理論的研究2007

    • Author(s)
      中田和秀等
    • Journal Title

      法政大学自然科学センター紀要 4(印刷中)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Aminolysis of Y-Substituted Phenyl X- Substituted Cinnamates and Benzoates : Effect of Modification of Nonleaving Group from Benzoyl to Cinnamoyl2007

    • Author(s)
      I.-H.Um et al.
    • Journal Title

      J.Org.Chem. 72,(in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Theoretical study of the substituent effect on the gas-phase acidities of dimethylanilinium ions2007

    • Author(s)
      K.Nakata et al.
    • Journal Title

      SRC Annual Report, Hosei Univ. Vol.4(in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] 環置換アニリニウムイオンの水中酸性度に及ぼす要因に関する理論的研究2006

    • Author(s)
      中田和秀等
    • Journal Title

      法政大学自然科学センター紀要 3

      Pages: 7-41

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The β-Silicon Effect. II. Substituent Effects on the Solvolysis of 1-Aryl-2-(aryldimethylsilyl)ethyl 3,5-Dinitrobenzoates2006

    • Author(s)
      M.Fujio et al.
    • Journal Title

      Bull. Chem. Soc. Jpn. 79・7

      Pages: 1091-1099

    • NAID

      10018001638

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Structure-reactivity correlations in nucleophilic substitution reactions of Y-substituted phenyl X-substituted benzoates with anionic and neutral nucleophiles2006

    • Author(s)
      I.-H.Um et al.
    • Journal Title

      Org. Biomol. Chem. 4・15

      Pages: 2979-2985

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Theoretical study of medium effect on the acidities of ring-substituted anilinium ions in water2006

    • Author(s)
      K.Nakata et al.
    • Journal Title

      SRC Annual Report, Hosei Univ. Vol.3

      Pages: 7-41

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The β-Silicon Effect. II. Substituent Effects on the Solvolysis of 1-Aryl-2-(aryldimethylsilyl)ethyl 3,5-Dinitrobenzoates2006

    • Author(s)
      M.Fujio et al.
    • Journal Title

      Bull.Chem.Soc.Jpn. 79-7

      Pages: 1091-1099

    • NAID

      10018001638

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Structure-reactivity correlations in nucleophilic substitution reactions of Y-substituted phenyl X-substituted benzoates with anionic and neutral nucleophiles2006

    • Author(s)
      I.-H.Um et al.
    • Journal Title

      Org.Biomol.Chem. 4-15

      Pages: 2979-2985

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The β-Silicon Effect 2. Substituent Effects on the Solvolysis Rate of 1-Aryl-2-(aryldimethylsilyl)ethyl 3,5-Dinitrobenzoates2006

    • Author(s)
      M.Fujio et al.
    • Journal Title

      Bull.Chem.Soc.Jpn. 79・7(in press)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] The Yukawa-Tsuno Relationship for the β-Silicon Effect in the Solvolysis of 2-(Aryldimethylsilyl)ethyl Chlorides2005

    • Author(s)
      M.Fujio et al.
    • Journal Title

      Bull. Chem. Soc. Jpn. 78・10

      Pages: 1834-1842

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A facile synthesis of fused spiroketal skeleton : 2,2'-Spirobi(4-aryl-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydrochroman)2005

    • Author(s)
      M.G.Ahmed et al.
    • Journal Title

      Tetrahedron Letters 46・47

      Pages: 8217-8220

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The Yukawa-Tsuno Relationship for the β-Silicon Effect in the Solvolysis of 2-(Aryldimethylsilyl)ethyl Chlorides2005

    • Author(s)
      M.Fujio et al.
    • Journal Title

      Bull.Chem.Soc.Jpn. 78-10

      Pages: 1834-1842

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A facile synthesis of fused spiroketal skeleton : 2,2'-Spirobi(4-aryl-7,7-dimethyl-5-oxo-5,6,7,8- tetrahydrochroman)2005

    • Author(s)
      M.G.Ahmed et al.
    • Journal Title

      Tetrahedron Letters 46-47

      Pages: 8217-8220

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The Yukawa-Tsuno Relationship for the β-Silicon Effect in the Solvolysis of 2-(Aryldimethylsilyl)ethyl Chlorides2005

    • Author(s)
      M.Fujio et al.
    • Journal Title

      Bull.Chem.Soc.Jpn. 78・10

      Pages: 1834-1842

    • Related Report
      2005 Annual Research Report
  • [Journal Article] A facile synthesis of fused spiroketal skeleton: 2,2'-Spirobi(4-aryl-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydrochroman)2005

    • Author(s)
      M.G.Ahmed et al.
    • Journal Title

      Tetrahedron Letters 46・47

      Pages: 8217-8220

    • Related Report
      2005 Annual Research Report

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Published: 2005-03-31   Modified: 2016-04-21  

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