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Studies on Sterically Protected Multiple Bonding Involving Low Coordinated Phosphorus Atoms

Research Project

Project/Area Number 02403008
Research Category

Grant-in-Aid for General Scientific Research (A)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionTOHOKU UNIVERSITY

Principal Investigator

YOSHIFUJI Masaaki  Tohoku University, Faculty of Science, Department of Chemistry, Professor, 理学部, 教授 (90011676)

Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥35,500,000 (Direct Cost: ¥35,500,000)
Fiscal Year 1991: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 1990: ¥29,500,000 (Direct Cost: ¥29,500,000)
KeywordsLow coordination / Steric protection / Organophosphorus compounds / Diphosphene / Diphosphaallene / Diphosphabutatriene / Phosphaalkyne / P-NMR / PーNMR
Research Abstract

Sterically protected phosphorus containing unusual compounds in low coordination states were prepared by utilizing the 2,4,6-tri-t-butylphenyl moiety (here abbreviated to the Ar group) as a protective group. Such unusual organophosphorus compounds as diphosphene (-P=P-), 1,3-diphosphaallene (-P=C=P-), and phosphaalkyne (-C*P) having low coordinated phosphorus atom(s) of coordination number 2 or 1 were isolated and characterized as kinetically stable compounds.
Protective groups other than the Ar group have been developed to utilize the stabilization of low coordinated organophosphorus compounds as follows. Attempts to prepare diphosphenes involving 2,6-di-t-butylphenyl, 2,4,6-tri-t-pentylphenyl, 1,2,3,4,5,6,7,8-octahydro-1,1,4,4,5,5,8,8-octamethyl-9-anthryl, and 2,4-di-t-butyl-6-dimethylaminophenyl were successful. Strong electron-withdrawing groups, such as 2,4,6-tris(trifluoromethyl)phenyl and 2,6-bis(trifluoromethyl)phenyl, were also useful as a protective auxiliary of diphosphenes as well as unsymmetrical diphosphenes.
A preparative method of 1,3-diphosphaallenes has been developed involving addition reaction of dichlorocarbene to diphosphenes leading to dichlorodiphosphiranes, which were further converted to diphosphaallenes with an appropriate alkyllithium reagent. This preparative method has been successful in preparation of some unsymmetrical diphosphaallenes' starting from unsymmetrical diphosphenes. Attempted preparations of the extended phosphacumulenes such as phosphabutatriene (-P=C=C=C ) and diphosphabutatriene (-P=C=C=P-) have been successful by this method.
A new preparative method of phosphaalkynes has been developed involving elimination and intramolecular rearrangement of 1-chloro-2-phosphaethenyllithiums and the ^<31>P NMR studies have been made in an attempt to observe intermediacy of phosphorus analogue of isonitrile during this unusual rearrangement reaction.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (48 results)

All Other

All Publications (48 results)

  • [Publications] T.Niitsu: "Preparation and Hydrolysis of Some Sterically Protected 3-Aza-1-phosphaallenes" Bull.Chem.Soc.Jpn.63. 2736-2738 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M.Yoshifuji: "Reactions of Halocarbenes with Phosphaalkyne.Formation of Acetylenes via Phosphirene Intermediates" Tetrahedron Lett.31. 6891-6892 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M.Yoshifuji: "Preparation of Sterically Protected 3,4-Bis(phosphinidene)cyclobutenes and their Isomerism" Chem.Lett.2195-2198 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M.Yoshifuji: "Reactions of Dichlorocarbene with Sterically Protected Phosphaallene and 1,3-Diphosphaallene" J.Chem.Soc.,Chem.Commun.124-125 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M.Yoshifuji: "Preparation of 1,4-Diphosphabutatriene from 3-Dichloromethylene-1,2-diphosphirane" Chem.Lett. 491-492 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Toyota: "Extremely Bulky Lithium Trialkylsilylphosphides.Synthetic Application to Sterically Protected Phosphaethylenes,Phosphaallenes,and Related Compound" Reviews on Heteroatom Chem. 5. 152-179 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M.Yoshifuji: "Preparation and Photolysis of Pentacarbonyl-tungsten Complex of Bis(2,4,6-tri-t-butylphenyl)diphosphene" Science Reports,Tohoku University,Ser.1. 73. 1-7 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Toyota: "Preparation of Group-6 Metal(0) Carbonyl Complexes of Chelate Type Containing Diphosphinidenecyclobutene as a Bidentate Ligand" Chem.Lett.2079-2082 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Toyota: "Reaction of Dichlorocarbene with Sterically Protected Phosphabutatriene.Formation of a Stable Dimethylenephosphirane" Tetrahedron Lett.32. 6879-6882 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Toyota: "Isolation and X-Ray Structure of trans-3,5-Bis(2,4,6-tri-t-butyl-phenyl)-1,2,3,5-dithiaphospholane 3,5-Disulfide" Chem.Lett.2213-2216 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] I.Miyahara: "The First X-Ray Analysis of a Phospa[3]radialene" Polyhedron. 11. 385-387 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Toyota: "Synthesis and X-Ray Structure Analysis of cis-2,4-Bis(2,4,6-tri-t-butylphenyl)-1,2,4-oxadiphosphetane 2,4-Disulfide" Heteroatom Chem.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M.Yoshifuji: "Preparation and Attempted Photoreaction of Diphosphenes Bearing 2,4,6-Tris(trifluoromethyl)phenyl Group" Science Reports,Tohoku University,Ser.1.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M.Yoshifuji: "Preparation of 2-Bromo-3,5-di-t-butyl-N,N-dimethylaniline.A Bulky Compound Potentially Applicable Steric Protection" Science Reports,Tohoku University,Ser.1.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Toyota: "Preparation and Isomerization of 3,4-Bis(2,4,6-tri-t-butylphenyl-phosphinidene)cyclobutenes" Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Toyota: "X-Ray Structure Analysis of a Diphosphinidenecyclobutene and Its Tetracarbonylmolybdenum(0) Comples of Chelata Type" J.Organomet.Chem.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M.Yoshifuji: "Multiple Bonds and Low Coordination in Phosphorus Chemistry;Ed.M.Regitz and O.J.Scherer" Georg Thieme Verlag,Stuttgart, 17 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M.Yoshifuji: "Multiple Bonds and Low Coordination in Phosphorus Chemistry;Ed.M.Regitz and O.J.Scherer" Gerog Thieme Verlag,Stuttgart, 4 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] T. Niitsu: "Preparation and Hydrolysis of Some Sterically Protected 3-Aza-1-phosphaallenes" Bull. Chem. Soc. Jpn.63. 2736 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshifuji: "Reactions of Halocarbenes with Phosphaalkyne. Formation of Acetylenes via Phosphirene Intermediates" Tetrahedron Lett.31. 6891 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshifuji: "Preparation of Sterically Protected 3,4-Bis(phosphinidene)cyclobutenes and their Isomerism" Chem. Lett.1990. 2195

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshifuji: "Reactions of Dichlorocarbene with Sterically Protected Phosphaallene and 1,3-Diphosphaallene" J. Chem. Soc. Chem. Commun.1991. 124

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshifuji: "Preparation of 1,4-Diphosphabutatriene from 3-Dichlorormethylene-1,2-diphosphirane" Chem. Lett.1991. 491

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Toyota: "Extremely Bulky Lithium Trialkylsilylphosphides. Synthetic Application to Sterically Protected Phosphaethylenes, Phosphaallenes, and Related Compounds" Review on Heteroatom Chemistry. 5. 152 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshifuji: "Preparation and Photolysis of Pentacarbonyl-tungsten Complex of Bis(2,4,6-tri-t-butylphenyl)diphosphene" Science Reports, Tohoku Univ., Ser. 1. 73. 1 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Toyota: "Preparation of Group-6Metal(0)Carbonyl Complexes of Chelate Type Containing Diphosphinidenecyclobutene as a Bidentate Ligand" Chem. Lett.1991. 2079

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Toyota: "Reaction of Dichlorocarbene with Sterically Protected Phosphabutatriene. Formation of a Stable Dimethylenephosphirane" Tetrahedron Lett.32. 6879 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Toyota: "Isolation and X-Ray Structure of trans-3,5-Bis(2,4,6-tri-t-butylphenyl)-1,2,3,5-dithiadiphospholane 3,5-Disulfide" Chem. Lett.1991. 2213

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] I. Miyayhara: "The First X-Ray Analysis of a Phospha[3]radialene" Polyhedron. 11. 385 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Toyota: "Synthesis and X-Ray Structure Analysis of cis-2,4-Bis(2,4,6-tri-t-butylphenyl)-1,2,4-oxadiphosphetane 2,4-Disulfide" Heteroatom Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshifuji: "Preparation and Attempted Photoreaction of Diphosphenes Bearing 2,4,6-Tris(trifluoromethyl)phenyl Group" Science Reports, Tohoku Univ., Ser. 1.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshifuji: "Preparation of 2-Bromo-3,5-di-t-butyl-N,N-dimethylaniline. A Bulky Compound Potentially Applicable to Steric Protection" Science Reports, Tohoku Univ., Ser. 1.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Toyota: "Preparation and Isomerization of 3,4-Bis(2,4,6-tri-t-butylphenyl-phosphinidene)cyclobutenes" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K. Toyota: "X-Ray Structure Analyses of a Diphosphinidene-cyclobutene and Its Tetracarbonylmolybdenum(0) Complex of Chelate Type" J. Organomet. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshifuji: "Phosphinylidenephosphines (Diphosphenes)" In "Multiple Bonds and Low Coordination in Phosphorus Chemistry," Ed. M. Regitz and O. J. Scherer, Georg Thieme Verlag, Stuttgart. 321-337 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] M. Yoshifuji: "Phosphinylidene-methylene (imino, oxo, thioxo, or selenoxo)phosphoranes" Ibid.411-414

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] K.Toyota,K.Tashiro,and M.Yoshifuji: "Preparation of Groupー6 Metal(0) Carbonyl Complexes of Chelate Type Containing Diphosphinidenecyclobutene as a Bidentate Liand" Chem.Lett.2079-2082 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] K.Toyota,H.Yoshimura,T.Uesugi,and M.Yoshifuji: "Reaction of Dichlorocarbene with Sterically Protected Phosphabutatriene.Formation of a Stable Dimethylenephosphirane" Tetrahedron Lett.32. 6879-6882 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] K.Toyota,Y.Ishikawa,M.Yoshifuji,K.Okada,K.Hosomi,and K.Hirotsu: "Isolation and XーRay Structure of iransー3,5ーBis(2,4,6ーtriーtーbutylphenyl)ー1,2,3,5ーdithiadiphospholane 3,5ーDisulfide" Chem.Lett.2213-2216 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] A.Hayashi,I.Miyahara,K.Hirotsu,M.Yoshifuji,H.Yoshimura,anシ K.Toyota: "The First XーRay Analysis of a Phospha〔3〕radialene" Polyhedron. 11. 385-387 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] M.Yoshifuji,K.Toyota,H.Yoshimura,K.Hirotsu,and A,Okamoto: "Reactions of Dichlorocarbene with Sterically Protected Phosphaallene and 1,3ーDiphosphaallene" J.Chem.Soc.Chem.Commun.124-125 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] M.Yoshifuji,K.Toyota,H.Yoshimura,K.Hirotsu,and A,Okamoto: "Preparation of 1,4ーDiphosphabutatriene from 3ーDichorormethyleneー1,2ーdiphosphirane" Chem.Lett.491-492 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] M.Yoshifuji: "Reaction of Dichlorocarbene with Phosphaethylene.Preparation of Phosphaallene from Phosphaethylene via Dichlorophosphirane" Chem.Lett.1990. 827-828 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Niitsu: "Preparation and Hydrolysis of Some Sterically Protected 3ーAzaー1ーphosphaallene" Bull.Chem.Soc.Jpn.63. 2736-2738 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.Yoshifuji: "Reactions of Halocarbenes with Phosphaalkyne.Formation of Acetylenes via Phosphirene Intermediates" Tetrahedron Lett.31. 6891-6892 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.Yoshifuji: "Preparation of Sterically Protected 3,4ーBis(phosphinidene)cyclobutenes and their Isomerism" Chem.Lett.1990. 2195-2198 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.Yoshifuji: "Reactions of Dichlorocarbene with Sterically Protected Phosphaallene and 1,3ーDiphosphaallene" J.Chem.Soc.,Chem.Commun.1991. 124-125 (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.Yoshifuji: "Preparation of 1,4ーDiphosphabutatriene from 3ーDichloromethyleneー1,2ーdiphosphirane" Chem.Lett.1991. 491-492 (1991)

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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