2005 Fiscal Year Final Research Report Summary
Novel Catalytic Heterofunctionalization of Unsaturated Hydrocarbons by Controlling Dynamic Complexes
| Project/Area Number |
14078217
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Kyoto University |
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Principal Investigator |
MITSUDO Take-aki Kyoto University, Graduate School of Engineering, Professor, 工学研究科・帰 (90026344)
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| Project Period (FY) |
2002 – 2005
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| Keywords | Ruthenium Complex / Water / Aqua Complex / Chiral / Metallacycle / Oxo Complex / DFT Calculation / Dynamic Behavior |
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| Research Abstract |
Synthesis, Structure, and Reactivity of a Stable Zerovalent Ruthenium Aqua Complex
Water is one of the most abundant substances in biological systems, where it acts as a solvent, reagent and architectural component. Although a water molecule has C_<2v> symmetry and is itself achiral, the oxygen atom of water can become a chiral center by coordination to a Lewis acid (transition metal) and by hydrogen bonding. However, there have no previously reported experimental evidences and concepts. We report the first synthesis and structure of an artificial model complex containing 'chiral water', Ru(dppe)(dmfm)_2(H_2O) (1) [dppe=1,2-bis(diphenylphosphino)ethane, dmfm=dimethyl fumarate] by reacting H_2O with Ru(η^6-cot)(dmfm)_2 (2) [cot=1,3,5-cyclooctatriene] and dppe. The dynamic behaviors of 1 in solution based on variable-temperature 1H NMR, line-shape analysis of the spectra, and DFT calculation are also disclosed.
Formation of Binuclear Ru(II) Aqua Complexes Bearing P-P-O Facial Tridentate Ligands and Oxametallacycle Moieties
The reaction of racemic Ru(η^6-cot)(dmfm)_2 (2) with water in the presence of either (S,S)-DIPAMP or o-MeO-dppe afforded unique binuclear Ru(II) aqua complexes 3, where two oxaruthenacycles are combined and hold a water molecule by coordination and two different hydrogen bonds. The molecular structures of 3 were revealed by X-ray crystallography.
Synthesis and Characterization of a Novel (μ3-Oxo)tetraruthenium Cluster
A novel (μ^3-oxo)tetraruthenium cluster (4) was synthesized in an isolate yield of 73% by the reaction of a zerovalent Ru(η^6-cot)(dmfm)2 (2) with water under reflux in 1,4-dioxane for 6 h. The X-ray structure of 4 as well as a possible formation mechanism has been disclosed.
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Research Products
(30 results)
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[Journal Article] Synthesis and Characterization of a Novel (μa-0xo)tetraruthenium Cluster2007
Author(s)
Teruyuki Kondo, Fumiaki Tsunawaki, Toshi-aki Suzuki, Yasuyuki Ura, Kenji Wada, Syuhei Yamaguchi, Hideki Masuda, Kenji Yoza, Motoo Shiro, Take-aki Mitsudo
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Journal Title
Journal of Organometallic Chemistry Vol. 692, No. 1-3
Pages: 530-535
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Formation of Divalent Ruthenacycles via Oxidative Cyclization of 1,3,5-Cyclooctatriene with Maleic Anhydride or Maleimides : An Intermediate for the Transition Metal-Mediated [6 + 2] Cycloaddition of 1,3,5-Trienes and Alkenes2006
Author(s)
Yasuyuki Ura, Taka-aki Utsumi, Hiroshi Tsujita, Kenji Wada, Teruyuki Kondo, Take-aki Mitsudo
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Journal Title
Organometallics Vol. 25, No. 12
Pages: 2934-2942
Description
「研究成果報告書概要(欧文)」より
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