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The significance of acid-base properties in the key ligand for hydrogenation: role of amido ligand
被引:0
作者:
Rawat, Kuber Singh
[1
]
Pathak, Biswarup
[1
,2
]
机构:
[1] Indian Inst Technol Indore, Discipline Chem, Indore 453552, Madhya Pradesh, India
[2] Indian Inst Technol Indore, Discipline Met Engn & Mat Sci, Indore 453552, Madhya Pradesh, India
关键词:
Density functional calculations;
hydrogenation;
formic acid;
heterolytic H-2 cleavage;
hydride transfer;
DENSITY-FUNCTIONAL THERMOCHEMISTRY;
LOW-PRESSURE HYDROGENATION;
MOLECULAR-ORBITAL METHODS;
CARBON-DIOXIDE;
CATALYTIC-HYDROGENATION;
PINCER LIGAND;
COMPUTATIONAL DESIGN;
CO2;
HYDROGENATION;
PENDANT AMINES;
IRON COMPLEXES;
D O I:
10.1007/s12039-018-1477-5
中图分类号:
O6 [化学];
学科分类号:
0703 ;
摘要:
Using the density functional theoretical calculations, a series of aliphatic amido pincer based Mn-complexes are proposed for base-free hydrogenation. We report here that the acid-base nature of the amido ligand plays a crucial role in heterolytic cleavage and proton transfer mechanism. The reaction free energy barrier values suggest that such amido ligand-assisted hydrogenation requires a lower activation barrier compared to the previously reported noble and non-noble metal-based catalysts. Furthermore, the Mn-NNN complex is the most promising catalyst by far and this could be due to the optimum acid-base nature of the amido ligand. Such acid-base properties of the pincer ligand can be tuned by ligand substitution, which in turn controls the catalytic activity. SYNOPSIS A series of aliphatic amido pincer ligand-based Mn-complexes are proposed for base-free hydrogenation. The acid-base nature of the amido ligand is very important in heterolytic cleavage and proton transfer mechanism. This acid-base property of the amido ligand plays a crucial role in base-free hydrogenation.
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页数:9
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