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

Formation of Unusual Valency by Heteroatom Interaction and Its Functional Capability

Research Project

Project/Area Number 03640435
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionUniversity of Tsukuba

Principal Investigator

FUJIHARA Hisashi  University of Tsukuba, Chemistry Assist.Professor, 化学系, 講師 (30190101)

Project Period (FY) 1991 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1993: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1992: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1991: ¥1,000,000 (Direct Cost: ¥1,000,000)
KeywordsHypervalent bond / Heteroatom / Transannular interaction / 酸化還元 / ジカチオン
Research Abstract

I have found that the transannular interaction between multi heteroatoms of cyclic chalcogenides can produce the dications and the hypervalent species. The results are summarized as follows.
The chemistry of hypervalent selenuranes is much less developed than that of sulfuranes, and sulfuranes with apical nitrogen ligands are little known. The three-center transannular interaction betwee selenium and two-nitrogen atoms of new N-benzyl derivatives of 1,11-(methanoaminomethano)-5H, 7H-dibenzo[b, g][1,5]selenazocine provides the stable aminoammonioselenurane which is a new type of an isolable cyclic diazaselenurane with two unsymmetrical apical nitrogen ligands of tertiary alkylamino and quaternary alkylammonio groups. Generally, selenuranes have two symmetrical electronegative groups such as oxygen or halogen atoms at the apical positions.
Much less is known about the chemistry of bis-hypervalent bouns with two adjacent hypervalent bonding species. Cyclic bis-telluride, 1,5-ditelluracyclo-octane reacted with halogens to give new dihalogenoditelluranes with a Te(IV)-Te(IV) bond. Reduction of the latter with aqueous NaOH, PhSH and SmI2 gave the neutral bis-telluride.

Report

(4 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • 1991 Annual Research Report
  • Research Products

    (30 results)

All Other

All Publications (30 results)

  • [Publications] Hisashi Fujihara: "Hypervalent Bond Formation and Interaction between Heavier Group 16 Elements in the Dihalides and Oxide of 5H,7H-Dibenzo[b,g][1,5]-ditellurocin and -telluraselenocin" Chemistry Lett.263-266 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "Preparation and Reactivity of Dichalcogenide(S,Se)Dication Salts from Medium-sized Cyclic Bis-sulfide and Bis-selenides" Tetrahedron. 49. 1605-1618 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "A New Mode for the Generation of o-Xylylene by peri-Selenium Participation from 8,13-Dihydrobenzo[g]naphtho[1,8-bc][1,5]diselenonin under Irradiation" J.Org.Chem.58. 5291-5292 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "Preparation and X-Ray Structure of 8,9,19,20-Tetrahydrodinaphtho[1',8'-jk;1,8-bc][1,5,9,13]tetraselenacyclohexadecine,and its Novel Ring Contraction in Concentrated Sulfuric Acid" J.Chem.Soc.,Perkin Trans.1. 2145-2146 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "A New Tetracoordinated Cyclic Diazaselenurane with Amino and Ammonio Groups as Two Unsymmetrical Apical Ligands and Its Bisammonioselenurane" J.Am.Chem.Soc.115. 9826-9827 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "Stereoselective Sulfur Extrusion Reaction of syn- and anti-10,20-Dibromo-2,3,12,13-Tetrathia[4.4]metacyclophanes to the Corresponding syn- and anti-Dithia[3.3]metacyclophanes" Heteroatom Chem.4. 487-490 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "Hypervalent Bond Formation and Interaction between Heavier Group 16 Elements in the Dihalides and Oxide of 5H, 7H-Dibenzo[b, g][1,5]-ditellurocin and -telluraselenocin" Chemistry Lett.263-266 (1933)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "Preparation and Reactivity of Dichalcogenide (S, Se) Dicaton Salts from Medium-sized Cyclic Bis-sulfide and Bis-selenides" Tetrahedron. 49. 1605-1618 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "A New Mode for the Generation of o-Xylylene by peri-Selenium Participation from 8,13-Dihydrobenzo[g]naphtho[1,8-bc][1,5]diselenonin under Irradiation" J.Org.Chem.58. 5291-5292 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "Preparation and X-Ray Structure of 8,9,19,20-Tetrahydrodinaphtho[1', 8'-jk ; 1,8-bc][1,5,9,13]tetraselenacyclohexadecine, and its Novel Ring Contraction in Concentrated Sulfuric Acid" J.Chem.Soc., Perkin Trans.1. 2145-2146 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "A New Tetracoordinated Cyclic Diazaselenurane with Amino and Ammonio Groups as Two Unsymmetrical Apical Ligands and Its Bisammonioselenurane" J.Am.Chem.Soc.115. 9826-9827 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "Stereoselective Sulfur Extrusion Reaction of syn- and anti-10,20-Dibromo-2,3,12,13-Tetrathia[4,4]metacyclophanes to the Corresponding syn- and anti-Dithia[3.3]metacyclophanes" Heteroatom Chem.4. 487-490 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hisashi Fujihara: "Hypervalent Bond Formation and Interaction between Heavier Group 16 Elements in the Dihalides and Oxide of 5H,7H-Dibenzo[b,g][1,5]-ditellurocin and -telluraselenocin" Chemistry Lett.263-266 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Hisashi Fujihara: "Preparation and Reactivity of Dichalcogenide(S,Se)Dication Salts from Medium-sized Cyclic Bis-sulfide and Bis-selenides" Tetrahedron. 49. 1605-1618 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Hisashi Fujihara: "A New Mode for the Generation of o-Xylylene by peri-Selenium Participation from 8,13-Dihydrobenzo[g]naphtho[1,8-bc][1,5]diselenonin under Irradiation" J.Org.Chem.58. 5291-5292 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Hisashi Fujihara: "Preparation and X-Ray Structure of 8,9,19,20-Tetrahydrodinaphtho[1',8'-jk;1,8-bc][1,5,9,13]tetraselenacyclohexadecine,and its Novel Ring Contraction in Concentrated Sulfuric Acid" J.Chem.Soc.,Perkin Trans.1. 2145-2146 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Hisashi Fujihara: "A New Tetracoordinated Cyclic Diazaselenurane with Amino and Ammonio Groups as Two Unsymmetrical Apical Ligands and Its Bisammonioselenurane" J.Am.Chem.Soc.115. 9826-9827 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Hisashi Fujihara: "Stereoselective Sulfur Extrusion Reaction of syn- and anti-10,20-Dibromo-2,3,12,13-Tetrathia[4.4]metacyclophanes to the Corresponding syn- and anti-Dithia[3.3]metacyclophanes" Heteroatom Chem.4. 487-490 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Hisashi Fujihara: "Migration of Acetoxy Group from Tetracoordinated Tellurium Compoundo 12,12-Diacetoxy-5H,7H-dibenzo[b,g][1、5]tellurathiocin, Induced by Transannular Te-S Interaction" Chemistry Lett.501-502 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hisashi Fujihara: "Hypervalent Selenurane with the Chalcogenium Cation(Se^+,S^+)from 1,11-(Methanoselenomethano)-5H,7H-dibenzo[b,g][1,5]diselenocin and Its Sulfur Derivative:Interconvertible Redox Structures by Multicenter Chalcogenide Participation" J.Am.Chem.Soc.114. 3117-3118 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hisashi Fujihara: "A New Oxidative Se-Dealkylation in Seleno-Pummerer Reaction of 1,8-Bis(methylseleno)naphthalene and Naphtho[1,8-b,c]-1,5-diselenocin Induced by Peri-Seleniu Participation" Chemistry Lett.1437-1440 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hisaashi Fujihara: "Disulfide Dications from Cyclic Bis-sulfides" Reviews on Heteroatom Chemistry. 6. 263-274 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hisashi Fujihara: "Formation of New Hydroxyselenonio and Hydroxyammonio-selenuranes from Reaction of Se-Oxides of 5H,7H-Dibenzo[b,g][1,5]diselenocine and N-Methyl-5H,7H-dibenzo[b,g][1,5]selenazocine with Silyl Triflates" J.Chem.Soc.,Perkin Trans.1,Perkin Commun.2247-2248 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hisashi Fujihara: "Preparation and Characterization of a Four-coordinated Ditellurane Stabilized by a Transannular Tellurium-Tellurium Bond from 1,5-Ditelluracyclooctane:A New Multicentre Hypervalent Species" J.Chem.Soc.,Perkin Trans.1,Perkin Commun.2583-2584 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hisashi Fujihara: "Formation,Characterization and Reactivity of a Selenaza Dication[R_2Se^+‐N^+R_3]from N‐Methyl‐5H,7H‐Dibenzo[b,g][1,5]selenazocine" J.Chem.Soc,.Chem.Commun.98-99 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Hisashi Fujihara: "A New Preparative Method and Reactivity of Diselenide Dication Salt from 5H,7H‐Dibenzo[b,g][1,5]diselenocine" J.Chem.Soc.,Chem.Commun.1052-1053 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Hisashi Fujihara: "Peri Interaction between Selenium Atoms in Dinaphtho[1,8‐b,c]‐1,5‐Diselenocin and 1,8‐Bis(methylseleno)naphthalene" Tetrahedron Lett.32. 4345-4348 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Hisashi Fujihara: "First Example of Tetraalkyl Substituted Ditelluride Dication Salt from 1,5‐Ditelluracyclooctane" Tetrahedron Lett.32. 4537-4540 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Hisashi Fujihara: "New Hypervalent σ‐Selenanes with a Transannular Se‐N Bond from N‐Methyl‐5H,7H‐dibenzo[b,g][1,5]selenazocine" J.Am.Chem.Soc.113. 6337-6338 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Hisashi Fujihara: "Synthesis of a New Tellurium Heterocycle,5H,7H‐Dibenzo[b,g][1,5]‐tellurathiocin,and Isolation and Reactivity of Its Tellurathia Dication Salt" Chemistry Lett.151-154 (1992)

    • Related Report
      1991 Annual Research Report

URL: 

Published: 1991-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi