| 研究課題/領域番号 |
18F18333
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| 研究機関 | 国立研究開発法人理化学研究所 |
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研究代表者 |
侯 召民 国立研究開発法人理化学研究所, 開拓研究本部, 主任研究員 (10261158)
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| 研究分担者 |
MO ZHENBO 国立研究開発法人理化学研究所, 開拓研究本部, 外国人特別研究員
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| 研究期間 (年度) |
2018-11-09 – 2021-03-31
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| キーワード | dinitrogen activation / hydrogenation / titanium / alkyl complex / hydride complex / dinitrogen complex / PNP ligation |
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| 研究実績の概要 |
Dinitrogen is one of the most plentiful molecules, but its thermodynamic stability and nonpolar nature make it unreactive. The conversion of molecular dinitrogen into more versatile molecules under ambient conditions is one of the most important chemical processes. Only a hand full of catalytic transformations of N2 to NH3 has been accomplished with molybdenum, iron, and cobalt complexes. These reaction systems generally require a stoichiometric excess of strong reducing agents and extra proton sources to afford NH3. An alternative approach is the direct reduction of N2 by transition metal complexes and dihydrogen, in which dihydrogen serves as both electron and proton sources. Very recently, our group discovered a new PNP-Ti system that can be applied in the cleavage and hydrogenation of N2 by H2. In this time, we isolated a side-on/end-on titanium dinitrogen complex by the hydrogenation of a titanium alkyl complex supported by a modified PNP ligation. The side-on/end-on titanium dinitrogen complex represents a good precursor for further dinitrogen cleavage and functionalization.
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| 現在までの達成度 (区分) |
現在までの達成度 (区分)
1: 当初の計画以上に進展している
理由
The goal of this research is to design molecular systems for the reduction of N2 to ammonia with H2 as electron source and hydrogen source. By tuning the steric and electronic properties of the complexes, the cleavage and hydrogenation of N2 by H2 under mild condition was achieved. This research can enrich our knowledge of dinitrogen activation chemistry, and more importantly, it may develop new routes for dinitrogen fixation under ambient condition.
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| 今後の研究の推進方策 |
1. Based on quantitative studies, unravel the mystery of how the N2 molecule is cleavage and development of new routes for dinitrogen fixation under ambient condition.
2. We also plan to design new N-heterocyclic carbene- and N-heterocyclic silylene-based CNC- and SiNSi-type pincer ligands as a tridentate ligand in place of the so far employed PNP-type pincer ligand for preparing new titanium systems for hydrogenation of N2 by H2. The stronger electron-donating ability of these ligands might render the new titanium systems high activity for dinitrogen activation.
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