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Crown Thioether Complexes of Low-valent Transition Metals

Research Project

Project/Area Number 60470048
Research Category

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

Allocation TypeSingle-year Grants
Research Field 無機・錯塩・放射化学
Research InstitutionUniversity of Osaka Prefecture

Principal Investigator

YOSHIDA Toshikatsu  Department of Chemistry, Faculty of Integrated Arts and Sciences, University of Osaka Prefecture, 総合科学部, 教授 (50029443)

Co-Investigator(Kenkyū-buntansha) AKACHI Tomohiro  Department of Chemistry, Faculty of Integrated Arts and Sciences, University of, 総合科学部, 助手 (20079057)
UEDA Tatsuo  Department of Chemistry, Faculty of Integrated Arts and Sciences, University of, 総合科学部, 助手 (90151795)
Project Period (FY) 1985 – 1987
Project Status Completed (Fiscal Year 1987)
Budget Amount *help
¥5,900,000 (Direct Cost: ¥5,900,000)
Fiscal Year 1987: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1986: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1985: ¥3,500,000 (Direct Cost: ¥3,500,000)
KeywordsCrown Thioether / Molybdenum Denitrogen Complex / Rhodium(I) Complexes / Ruthenium(II) Hydrides / Intermolecular C(sp^2)-H Bond Activation / C(SP^2)-H結合活性化 / ヒドリド錯体 / 配位窒素分子のアリール化 / Rh(【I】)クラウンチオエーテル錯体 / ring size効果 / Mo(【II】)クラウンチオエーテル錯体 / 酸素錯体 / CO錯体
Research Abstract

Avariety of low-valent transition metal complexes of crown thioethers such as 1,4,8,11-tetrathia- cycloteetradecane ([14]aneS_4), its 6,6,13,13-tetramethyl analogue (Me_4[14]aneS_4), 1,5,9,13-terathiachclo-hexadecane ([16]aneS_4), and its 3,3,7,7,11,11,15,15-octamethy analogue (Me_8[16]aneS_4) have been prepared. They are RhL^+ (L=R_4[14]aneS_4, R_8[16]aneS_4), cis- and trans-RuCl_<>L (L=R_4[14]aneS_4,R_8[16]aneS_4), trans-RuH(C1)L (L=Me_4[14]aneS_4,Me_8[16]aneS_4), trans-RuH(BH_4,Ru_2H(C1)(<nu>-H) [Me_4[14]aneS_4]_2^+, and trans-MoL_2Me_8[16]aneS_4 (L'=Cl, Br, N_2, CO, HC<congruent>CH, PhC<congruent>CH, CH_2=CH_2). The elctrochemical, spectral, and x-ray structural studies of these complexes as well as extended Huckel MO calculations on the models, RH(SH_2)_4)^+ and trans-Mo(N_2)_2(SH_2)_4 revealed that the crown thioethers behave as p_<<pi>> donor ligand. this eelctronic feature of the crown thioether was further verified by the facile oxidative addition of CH_2Cl_2 to give trans-RHCl(CH_2Cl)L^+ and also by an unpercedented direct arylation of the coordinated N_2 molecule in trans-Mo(N_2)_2Me_8[16]aneS_4 with PhX under ambient conditions affording trans-MoX(N_2Ph)Me_8[16]-aneS_4 (X=Br, I). The chemical properties of the above complexes are found to be affected by the ring size of the macrocycles and the geometry of the complexes. For example, a reaction of cis-RuCl_2R_4[14]-aneS_4 with Al_2Me_6 in aromatic hydrocarbons proceeds through an intermolecular C(sp^2)-H bond activation to give trans-RuCl(Ar)R_4[14]aneS_4 (Ar=Ph, tolyl), while a similar reaction of trans-isomer afforded trans-MoCl(Me)Me_4[14]aneS_4. By contrast, cis-RuCl_2Me_8[16]aneS_4 gave an expected RuCl(Me_8[16]aneS_4. It is to be noted that trans-Mo(N_2)_2Me_8[16]aneS_4 represents the first example of dinitrogen complex containing only sulfur ligand which has been long desired to prepared as a chemical model to mimic the function of nitrogenase.

Report

(2 results)
  • 1987 Final Research Report Summary
  • 1986 Annual Research Report
  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] T. Yoshida;T. Ueda;T. Adachi;K. Yamamoto;K. Hirotsu;T. Higuchi: J. Chem. Soc. Chem. Commun.1137-1138 (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] T. Yoshida;T. Adachi;T. Ueda;M. Watanabe;M. Kaminaka;T. Higuchi: Angew. Chem. Int. Ed. Engl.26. 1171-1172 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] T. Ueda;H. Yamanaka;T. Adachi;T. Yoshida: Chem. Lett.525-526 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] T.Yoshida, T.Ueda, T.Adachi, K.Yamamoto, K.Hirotsu, and T.Higuchi: "Cationic Rhodium(I) Complexes of 1,4,8,11-Tetrathiacyclotetradecane([14]aneS_4) and 6,6,13,13-Tetramethyl Analogue (Me_4[14]aneS_4). Preparation of Two Conformers, X-Ray Crystal Structure of (Rh[14]aneS_4)_2Cl_2.MeCN, and Coformational Effect on the Nucleo- philicity of Rhodium(I) Ion" J. Chem. Soc. Chem. Commun.1137-1138 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] T.Yoshida, T.Adachi, T.Ueda, M.Watanabe, M.Kaminaka, and T.Higuchi: "Low-valent Molybdenum(II and O) Complexes of 3,3,7,7,11,11,15,15-Octamethyl- 1,5,9,13-tetrathiacyclohexadecane" Angew. Chem. Int. Ed. Engl.26. 1171-1172 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] T.Ueda, H.Yamanaka, T.Adachi, and T.Yoshida: "Methyl and Aryl Ru(II) Complexes of Crown Thioethers R_4[14]aneS_4 (R=H,Me). Remarkable Geometrical Effect on Intermolecular C(sp^2)-H Bond Activation by cis- and trans-RuCl_2R_4[14]aneS_u-Al_2Me_6" Chem.Lett.525-526 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary

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Published: 1987-03-31   Modified: 2016-04-21  

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