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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