Development of efficient oxidation catalysts with cheap oxidants
| Project/Area Number |
26630414
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Multi-year Fund |
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| Research Field |
Catalyst/Resource chemical process
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| Research Institution | Doshisha University |
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Principal Investigator |
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| Project Period (FY) |
2014-04-01 – 2017-03-31
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| Project Status |
Completed (Fiscal Year 2016)
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| Budget Amount *help |
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2016: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2015: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2014: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
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| Keywords | 可溶性メタンモノオキシゲナーゼ / 酸素分子活性化 / 安価な酸化剤 / カルボキシル基含有二核化配位子 / アルカン水酸化 / カルボキシラト基の効果 / A/K比 / 触媒回転数 / 酸化システムの開発 / カルボキシラトリッチな配位環境 / カルボキシラト基を持つ二核化配位子 / アルカン類の酸化反応 / カルボン酸含有二核鉄錯体 / 側鎖アルキル基の疎水性 / 高い触媒能力 / 過酸化水素 / 二核鉄錯体 / シクロヘキサン / アダマンタン / ３級／２級の選択性 / 酸化活性種 / syn-to-anti構造変化 / 反応速度の大きな加速 / 大きな同位体効果 / 高性能酸化触媒 / アルカン活性化 / high-spin diiron(IV) |
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| Outline of Final Research Achievements |
Soluble methane monooxygenases (sMMO) are nonheme diiron enzymes that catalyze oxidation of various organic compounds. Diiron centers of sMMO are coordinated by two imidazole donors of His residues and by four carboxylate donors of Glu residues. In this study we synthesized four different carboxylate-rich dinucleating ligands, 1,2-bis(N-benzyl-2-amino- methyl-6-pyridyl)ethane-N,N’-diglycine (H2Lgly), 1,2-bis(6-aminomethyl-2-pyridyl)ethane-N,N’-di- (norleucine) (H2Lnle), 1,2-bis(6-aminomethyl-2-pyridyl)ethane-N,N’-di(N-methylnorleucine) (H2LMenle), 1,2-bis(N-(9-anthracene)-2-aminomethyl-6-pyridyl)ethane (H2Lanthracenegly). These ligands form diiron complexes, which rapidly and efficiently catalyzed the oxidation of alkanes with m-CPBA as an oxidant to show high A/K ratio, large turnover number, large turnover frequency in the catalytic oxidations. These are attained by the carboxylate-rich coordination environment.
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Report
(4 results)
Research Products
(36 results)
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[Journal Article] Roles of Carboxylate Donors in O-O Bond Scission of Peroxodiiron(III) to High-Spin Oxodiiron(IV) with a New Carboxylate-Containing Dinucleating Ligand2014
Author(s)
M. Kodera, T. Tsuji, T. Yasunaga, Y. Kawahara, T. Hirano, Y. Hitomi, T. Nomura, T. Ogura, Y. Kobayashi, Sajith P. K., Y. Shiota, and K. Yoshizawa
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Journal Title
Chem. Sci.
Volume: 5
Issue: 6
Pages: 2282-2292
DOI
Related Report
Peer Reviewed / Acknowledgement Compliant
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