• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

STRACTURAL INVESTIGATION OF GRIGNARD REAGENTS BY MEANS OF SPRAY IONIZATION MASS SPECTROMETRY AND RAPID X-RAY CRYSTALLOGRAPHY

Research Project

Project/Area Number 10671983
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionChiba University

Principal Investigator

YAMAGUCHI Kentaro  CHEMICAL ANALYSIS CENTER, CHIBA UNIVERSITY, ASSOCIATE PROFESSOR, 分析センター, 助教授 (50159208)

Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1999: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1998: ¥1,200,000 (Direct Cost: ¥1,200,000)
KeywordsGrignard reagent / X-ray crystallography / ESI-MS / equilibrium / CCD回折計 / 有機金属試薬
Research Abstract

The cold ESI, operating ionization under low temperature was recently developed in our laboratory and proved to be effective to preserve thermally unstable compounds unchanged. Some significant spectra were obtained form MeMgCl, MeMgBr, EtMgCl, EtMgBr, PhMgCl t-BuMgCl, AllyMgCl and i-PrMgCl in tetrahydrofuran (THF) solution using the cold ESI. The characteristic ion peaks consistent with these three spectra of m/z 529, 601 and 673 indicate the ion species of [NMgィイD22ィエD2ClィイD23ィエD2(THF)ィイD2nィエD2]ィイD1+ィエD1 formed based on the atomic nitrogen attached break down products. The [RMgィイD22ィエD2ClィイD23ィエD2(THF)ィイD2nィエD2-H]ィイD1+ィエD1 ion peaks directly related to the corresponding Grignard species are definitely observed in EtMgCl and PhMgCl. The isotopic ion peak patterns as well as MS/MS analysis detecting sequential THF cleavage from the parent ion suggest these ion structures. Following equilibrium is then derived.
3RMgX(THF)ィイD2nィエD2【double arrow】RィイD22ィエD2Mg + RMgィイD22ィエD2XィイD23ィエD2(THF)ィイ … More D2nィエD2 (eq.1)
On the other hand, X-ray crystallographic analyses were undertaken. We determined the crystal structures of 2[MgィイD22ィエD2ClィイD23ィエD2(THF)ィイD26ィエD2]・[PhィイD24ィエD2MgィイD22ィエD2ClィイD22ィエD2] obtained from PhMgCl, and [MgィイD22ィエD2ClィイD23ィエD2(THF)ィイD26ィエD2]・[t-BuMgClィイD22ィエD2(THF)] from t-BuMgCl. The structure of dimagnesium cationic species included in the both crystals obtained from PhMgCl and t-BuMgCl was solved. This cationic species [MgィイD22ィエD2ClィイD23ィエD2(THF)ィイD26ィエD2]ィイD1+ィエD1 which is detected in the Grignard reagent for the first time has rarely observed. The first crysta lstructure of RMgX without solvent molecule was observed. In case of the crystal obtained from t-BuMgCl, monomeric structure (t-BuMgClィイD22ィエD2THF) was observed together with the cationic species. These constitutions were thought to be included in the Schlenk equilibrium.
8PhMgCl(THF)ィイD2nィエD2 【double arrow】2PhィイD22ィエD2Mg + 2[(MgィイD22ィエD2ClィイD23ィエD2)(THF)ィイD26ィエD2]ィイD1+ィエD1 + [PhィイD24ィエD2MgィイD22ィエD2ClィイD22ィエD2]ィイD12-ィエD1 (eq. 2)
5t-BuMgCl(THF)ィイD2nィエD2 【double arrow】 2t-BuィイD22ィエD2Mg + [(MgィイD22ィエD2ClィイD23ィエD2)(THF)ィイD26ィエD2]ィイD1+ィエD1 + [t-BuMgClィイD22ィエD2(THF)]ィイD1-ィエD1 (eq. 3)
Other crystal structures of Grignard species have also been investigated in the same manner for comparison. In case of MeMgCl, the crystal structure of MeィイD22ィエD2MgィイD24ィエD2ClィイD26ィエD2(THF)ィイD26ィエD2 included in Schlenk equilibrium was found.
6MeMgCl(THF)ィイD2nィエD2 【double arrow】 2MeィイD22ィエD2Mg + MeィイD22ィエD2MgィイD24ィエD2ClィイD26ィエD2(THF)ィイD26ィエD2 (eq. 4) Less

Report

(3 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] S.-G.Roh,K.-M.Park,G.-J.Park,S.Sakamoto,K.Yamaguchi and K.Kim: "Synthesis of a Five-Membered Molecular Necklace[5]MN : A2+2 approach"Angew. Chem. Int. Ed.. 38. 637-641 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H.Kagechica,I.Azumaya,A.Tanatani,K.Yamaguchi and K.Shudo: "A Layered Artifical Dinucleotide Complex"Tetrahedron Lett.. 40. 3423-3426 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N.Takeda,K.Umemoto,K.Yamaguchi and M.Fujita: "A nanometer-sized hexahedral coordination capsule assembled from 24 components"Nature. 398. 794-796 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Fujita,N.Fujita,K.Ogura and K.Yamaguchi: "Spontaneous assembling of ten components into two interlockde identical coordination cages"Nature. 400. 52-55 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H.Tsuruta,K.Yamaguchi and T.Imamoto: "Evaluation of the Relative Lewis Acidities of Rear Earth (III) Compounds by Tandem Mass Spectrometry"Chem. Commun.. 1999. 1703-1704 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K.Tashiro,T.Aida,J.-Y.Zheng,K.Kinbara,K.Saigo,S.Sakamoto and K.Yamaguchi: "A Cyclic Dimer of Metalloporphyrin Forms a Highly Stable Inclusion Complex with C60"J. Am. Chem. Soc.. 121. 9477-9478 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K.Yamaguchi,S.Sakamoto,T.Imamoto and S.Ishikawa: "Internal Calibrant for Exact Mass Measurement in Electrospray Inization Mass Spectrometry"Anal. Sci.. 15. 1037-1038 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] F.Ibukuro,M.Fujita,K.Yamaguchi and J.-P.Sauvage: "Quantitative and Spontaneous Formation of a Doubly Interlocking [2] Catenane Using Copper(I) and Palladium(II) as Templating and Assembling Centers"J. Am. Chem. Soc.. 121. 11014-11015 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S.Sakamoto,M.Fujita,K.Kim and K.Yamaguchi: "Characterzation of Self-assembling Nano-sized Structures by Means of Coldspray Ionization Mass Spectrometry"Tetrahedron. 56. 955-964 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. -G. Roh, K. -M. Prak, g. -J. Park, S. Sakamoto, K. Yamaguchi and K. Kim: "Synthesis of a Five-Membered Molecular Necklace[5]MN : A2+2 approach."Angew. Chem. Int. Ed.. 38. 637-641 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H. Kagechika, I. Azumaya, A. Tanatani, K. Yamaguchi and K. Shudo: "A Layered Artificial Dinucleotide Complex."Tetrahedron Lett.. 40. 3423-3426 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Takeda, K. Umemoto, K. Yamaguchi & M. Fujita: "A nanometer-sized hexahedral coordination capsule assembled from 24 components."Nature. 398. 794-796 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Fujita, N. Fujita, K. Ogura and K. Yamaguchi: "Spontaneous assembling of ten components into two interlocked identical coordination cages."Nature. 400. 52-55 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H. Tsuruta, K. Yamaguchi and T. Imamoto: "Evaluation of the Relative Lewis Acidities of Rear Earth (III) Compounds by Tandem Mass Spectrometry."Chem. Commun.. 1999. 1703-1704 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K. Tashiro, T. Aida, J-Y. Zheng, K. Kinbara, K. Saigo, S. Sakamoto and K. Yamaguchi: "A Cyclic Dimer of Metalloporphyrin Forms a Highly Stable Inclusion Complex with C60."J. Am. Chem. Soc.. 121. 9477-9478 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K. Yamaguchi, S. Sakamoto, T. Imamoto and S. Ishikawa: "Internal Calibrant for Exact Mass Measurement in Electrospray Inization Mass Spectrometry."Anal. Sci.. 15. 1037-1038 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] F. Ibukuro, M. Fujita, K. Yamaguchi, and J. -P. Sauvage: "Quantitative and Spontaneous Formation of a Doubly Interlocking [2]Catenane Using Copper(I) and Palladium(II) as Templating and Assembling Centers."J. Am. Chem. Soc.. 121. 11014-11015 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S. Sakamoto, M. Fujita, K. Kim and K. Yamaguchi: "Characterization of Self-assembling Nano-sized Structures by Means of Coldspray Ionization Mass Spectrometry."Tetrahedron in. 56. 955-964 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] S.-G. Roh, K.-M. Park, G.-J. Park, S. Sakamoto, K. Yamaguchi and K. Kim: "Synthesis of a Five-Membered Molecular Necklace[5]MN:A2+2 approach"Angew. Chem. Int. Ed.. 38. 637-641 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Kagechika, I. Azumaya, A. Tanatani, K. Yamaguchi and K. Shudo: "A Layered Artificial Dinucleotide Complex"Tetrahedron Lett.. 40. 3423-3426 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] N. Takeda, K. Umemoto, K. Yamaguchi and M. Fujita: "A nanometer-sized hexahedral coordination capsule assembled from 24 components"Nature. 398. 794-796 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M. Fujita, N. Fujita, K. Ogura and K. Yamaguchi: "Spontaneous assembling of ten components into two interlockde identical coordination cages"Nature. 400. 52-55 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H. Tsuruta, K. Yamaguchi and T. Imamoto: "Evaluation of the Relative Lewis Acidities of Rear Earth (III) Compounds by Tandem Mass Spectrometry"Chem .Commun.. 1999. 1703-1704 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Tashiro, T. Aida, J.-Y. Zheng, K. Kinbara, K. Saigo, S. Sakamoto and K. Yamaguchi: "A Cyclic Dimer of Metalloporphyrin Forms a Highly Stable Inclusion Complex with C60"J. Am. Chem. Soc.. 121. 9477-9478 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Yamaguchi, S. Sakamoto, T. Imamoto and S. Ishikawa: "Internal Calibrant for Exact Mass Measurement in Electrospray Inization Mass Spectrometry"Anal. Sci.. 15. 1037-1038 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] F. Ibukuro, M. Fujita, K. Yamaguchi and J.-P. Sauvage: "Quantitative and Spontaneous Formation of a Doubly Interlocking [2] Catenane Using Copper(I) and Palladium(II) as Templating and Assembling Centers"J. Am. Chem. Soc.. 121. 11014-11015 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] S. Sakamoto, M. Fujita, K. Kim and K. Yamaguchi: "Characterization of Self-assembling Nano-sized Structures by Means of Coldspray Ionization Mass Spectrometry"Tetrahedron. 56. 955-964 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] K.Yamaguchi,S.Sakamoto,H.Tsuruta and T.Imamoto: "Atomic Nitrogen Adducts Formation at SP^3 Carbon in the Electrospray" Clem.Commun.1998. 2123-2124 (1998)

    • Related Report
      1998 Annual Research Report

URL: 

Published: 1998-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi