| Project/Area Number |
16350035
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Tokyo University of Science |
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Principal Investigator |
HIDAI Masanobu Tokyo University of Science, Faculty of Industrial Science and Technology, Professor, 基礎工学部, 教授 (60011011)
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| Co-Investigator(Kenkyū-buntansha) |
SUZUKI Toshiaki RIKEN, Senior Research Scientist, 侯有機金属化学研究室, 先任研究員 (20332257)
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| Project Period (FY) |
2004 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥12,000,000 (Direct Cost: ¥12,000,000)
Fiscal Year 2005: ¥4,600,000 (Direct Cost: ¥4,600,000)
Fiscal Year 2004: ¥7,400,000 (Direct Cost: ¥7,400,000)
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| Keywords | thiacalixarene / sulfur / multimetallic complex / early-late heterobimetallic complex / チタン / ロジウム / C-O結合切断 / C-S結合切断 / 前周期-後周期 / 異種複核錯体 / ELHB錯体 / ルテニウム / イリジウム / ニオブ / モリブデン / 窒素固定 |
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| Research Abstract |
Sulfur-containing thiacalix[4]arene and its derivatives are expected to react with transition metal complexes to form various types of mononuclear and multimetallic complexes with a thiacalix[4]arene cavity. These complexes might provide unique reaction sites for chemical transformations. We have here revealed the difference in reactivities of thiacalix[4]arenes towards various transition metal complexes.
The reactions of [Cp^*MCl_2]_2 (Cp^*=η^5-C_5Me_5,M=Rh,Ir) with thiacalix[4]arene (TC4A(OH)_4) and tetramercaptothiacalix[4]arene (TC4A(SH)_4) gave the mononuclear complexes [(Cp^*M){η^3-TC4A(OH)_2(O)_2}] and the dinuclear complexes [(Cp^*M)_2{η^3:η^3-TC4A(S)_4}], respectively, while the analogous reactions with dimercaptothiacalix[4]arene (TC4A(OH)_2(SH)_2) produced the tetranuclear complexes [(Cp^*M)_2(Cp^*MCl_2)_2{η^3:η^3:η^1:η^1-TC4A(O)_2(S)_2}], which formed via [(Cp^*MCl)_2{η^2:η^2-TC4A(OH)_2(S)_2}] and [(Cp^*M)_2{η^3:η^3-TC4A(O)_2(S)_2}].
The early-late heterobimetallic (ELHB) complexes were obtained from the reaction of [(CpM^1Cl_2){η^3-TC4A(OH)_2(O)_2} (M^1=Nb,Ta) with [Cp^*M^2Cl_2]_2 (M^2=Rh, Ir) in the presence of NEt_3. The reaction of [(CpTi){TC4A(OH)(O)_3}] with [RuHCl(PPh_3)_3] in the presence of NaH gave an octanuclear Ti_2Ru_2Na_4 complex.
A stepwise reaction of thiacalix[4]arene (TC4A(OH)_4) with [CpTiCl_3]-NEt_3 and cis-[Mo(N_2)_2(PMe_2Ph)_4] afforded a new Ti-Mo heterobimetallic complex [Ti(μ_2-C_5H_5)MoH(PMe_2Ph)_2{TC4A(O)_4}] which shows an unusual α-agostic μ^2-η^5:η^2-coordination of a cyclopentadienyl ligand to both Ti and Mo.
The present work demonstrates the usefulness of thiacalix[4]arene and its derivatives as excellent ligands for the synthesis of multimetallic complexes and activation of substrates on the multimetallic sites.
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