Theoretical Insights into Transition Metal-Catalyzed Reactions of Carbon Dioxide

Theoretical Insights into Transition Metal-Catalyzed Reactions of Carbon Dioxide 

Chemical transformation of carbon dioxide has attracted considerable interest because it presents possibilities of converting it into new chemical products and of reducing its concentration in the earths atmosphere [1]. In the chemical community, enormous efforts have been made to develop low-cost and catalyt-ically effective transition metal catalysts and reagents for the transformation of carbon dioxide [2]. Over the years, tremendous progresses have been made in understanding its reactions with various transition metal complexes [3]. At the same time, various interesting catalytic conversions of CO2 have also been discovered. 

In this chapter, we discuss theoretical studies of some selected transition metal-catalyzed reactions of carbon dioxide to illustrate how important concepts and insights can be derived as a result of these studies. These selected reactions include hydrogenation of CO2 with Hj, coupling reactions of COj and epoxides, reduction of CO2 with organoborons, carboxylation of olefins with COj, and hydrocarboxy-lation of olefins with CO2 and Hj. They are fundamentally important reactions of carbon dioxide and have been intensively investigated experimentally and theoretically. This chapter is not intended to be a comprehensive review. Instead, we discuss the above-mentioned selected examples that we believe to be representative and important in the area of homogeneous catalysis of COj by transition metals from our own perspective. 

Understanding Organometallic Reaction Mechanisms and Catalysis Computational and Experimental Tools, First Edition. Edited by Valentine R Ananikov. 

Hydrogenation of CO2 to formic acid (H2 -I- CO2 - HC(O)OH) catalyzed by transition metal complexes is one of interesting and attractive reactions for COj fixation. Experimentally, various metal complexes, especially those of Ru and Rh, have been found to be able to efficiently catalyze this reaction [10]. Studies show that metal hydride complexes display excellent catalytic activity. This is understandable as reactions of metals with Hj easily generate metal hydride species. Computationally, hydrogenation of COj to formic acid is also among one of the most studied reactions involving COj [11,12]. 

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I 6 Theoretical Insights into Transition Metal-Catalyzed Reactions of Carbon Dioxide 6.2... 

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