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Synthesis of New Transition Metal Carbene Complexes Using the Caracteristics of Hypervalent Sulfur and Its applications

Research Project

Project/Area Number 06640696
Research Category

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

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionUniversity of Osaka Prefecture

Principal Investigator

MATSUMURA Noboru  University of Osaka Prefecture, College of Engineering, research Associate, 工学部, 助手 (40125274)

Co-Investigator(Kenkyū-buntansha) INOUE Hiroo  University of Osaka Prefecture, College of Engineering, Professor, 工学部, 教授 (10081316)
Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1995: ¥200,000 (Direct Cost: ¥200,000)
Fiscal Year 1994: ¥2,100,000 (Direct Cost: ¥2,100,000)
Keywords10-S-3 Tetraazapentalene derivatives / Hypervalent sulfur / Trithiadiazapentalene derivatives / Thiadiselenadiazapentalene derivatives / Transition Metal Carbene Complexes / カルベン錯体 / アザクラウンエーテル / アザチアクラウンエーテル
Research Abstract

The reactions of pi-sulfurane compounds with low valence transition metal complexes were in investigated. The results obtained are summarized below.
1.10-S-3 Tetraazapentalene derivatives reacted with Pd (PPh_3)_4, Pt (PPh_3)_4, and RhCl (PPh_3)_3 to give the carbene complexes of the [N-M-S] and/or [S-M-S] types (M=Pd, Pt, Rh) , respectively, accompanying the formation of triphenyl phosphine sulfide in the same ammount as that of the carbene complexes.
2. The structure of carbene complexes was determined by X-ray analysis. The Pd atom of [S-Pd-S] type has a square planar-coordinated structure surrounded by two sulfur ligands, one phosphorus ligand, and one carbene ligand. The structure of carbene complex of [N-Pd-S] type was determined by comparison of its spectral data with those of the carbene complexes of [S-Pd-S] type. The structure of Pt (II) carbene complex was similar to the structure of Pd (II) carbene complex.
3. The [N-Pd-S] type-carbene complex is stable to air in solid state but unstable in organic solvents at room temperature. Namely, the [N-Pd-S] type-carbene complex was completely converted into [S-Pd-S] type-carbene complex in refluxed benzene.
4. The X-ray crystallographic analysis of Rh (III) carbene complex showed the following structural features. (i) The Rh atom is octahedrally coordinated. (ii) The six coordinated-sites are occupied by one chloro ligand, two trans phosphine ligands, and one tridentate ligand formed by release of hypervalent sulfur. (iii) The C (1)-Rh bond length is very similar to that of known Rh (III) carbene complexes. (iv) This carbene complex is stable under air atmosphere.
5. Trithia-and thiadiselena-diazapentalene derivatives also reacted with Pd (PPh_3) _4, Pt (PPh_3) _4, and RhCl (PPh_3) _3 to give the carbene complexes of [Y-M-Y] types (Y=S or Se, M=Pd, Pt, Rh) , respectively, together with S=PPh_3.

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (7 results)

All Other

All Publications (7 results)

  • [Publications] Noboru Matsumura, Ryuji Hirase, and Hiroo Inoue: "Synthesis of New Azacrown and Azathiacrown Ethers Using a Hypervalent Sulfur-Containing Tetraazapentalene as a Ring-Building Block" Tetrahedron Lett. 35. 899-902 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Noboru Matsumura, Jun-ichi Kawano, Noriki Fukunishi, Hiroo Inoue, Masanori Yasui, and Fujiko Iwasaki: "Synthesis of New Transition Metal Carbene Complexes from pi-Sulfurane Compounds : Reaction of 10-S-3 Tetraazapentalene Derivatives with Pd (PPh_3) _4 and RhCl (PPh_3) _3" J.Am.Chem.Soc. 117. 3623-3624 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Noboru Matsumura, Motoyuki Kusamiya, and Hiroo Inoue: "Synthesis and Reactivities of 10-S-3 Trithiadiazapentalene Derivatives" J.Heterocycl.Chem. 32. 1269 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Noboru matsumura(松村昇): "Synthesis of New Azacrown and Azathiacrown Ethers Using a Hypervalent Sulfur-Containing Tetraazapentalene as a Ring-Building Block" Tetrahedron Letters. 35. 899-902 (1994)

    • Related Report
      1995 Annual Research Report
  • [Publications] Noboru matsumura(松村昇): "Synthesis of New Transition Metal Carbene Complexes from π-Sulfurane Compounds" Journal of the American Chemical Society. 117. 3623-3624 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Noboru matsumura(松村昇): "Synthesis and Reactivities of 10-S-3 Trithiadiazapentalene Derivatives" Journal of Heterocyclic Chemistry. 32. 1269-1275 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Noboru Matsumura(松村 昇): "Synthesis of New Azacrown and Azathiacrown Ethers Using a HypervalentSulfur-Containing Tetraazapentalene asa Ring-Building Block" Tetrahedron Letters. 35. 899-902 (1994)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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