Flexible proton-responsive ligand-based Mn(I) complexes for CO2 hydrogenation: a DFT study

被引：10

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

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2018年 / 20卷 / 18期

关键词：

EFFECTIVE CORE POTENTIALS; CARBON-DIOXIDE HYDROGENATION; LOW-PRESSURE HYDROGENATION; MOLECULAR-ORBITAL METHODS; FORMIC-ACID; CATALYTIC-HYDROGENATION; COMPUTATIONAL DESIGN; MECHANISTIC INSIGHT; FREE-ENERGIES; IRON;

D O I：

10.1039/c7cp08637g

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A series of flexible proton-responsive group substituted N<^>N-bidentate ligand based Mn(I) complexes have been studied for base free CO2 hydrogenation. We show here that proton responsive ligands play a critical role in base free CO2 hydrogenation. Our calculated reaction free energy barrier values for heterolytic H-2 cleavage show that such flexible proton-responsive ligands require a very low activation energy (similar to 3 kcal mol(-1)) barrier. Such flexible proton responsive ligands improve the strong dihydrogen ( H center dot center dot center dot H) bonding, which in turn improves heterolytic H-2 cleavage - an important step for base free CO2 hydrogenation. Therefore, we believe that such flexible proton responsive ligand-substituted metal complexes can be promising for base free CO2 hydrogenation reactions.

引用

页码：12535 / 12542

页数：8

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