Transition metal catalyzed cross-coupling and nitrogen reduction reactions: Lessons from computational studies

Quantitative details of the reaction mechanisms of transition metal homogeneous catalysis can be determined from modern computational methods. A computed reaction mechanism gives an atomic-scale picture of the chemical events of the catalytic processes. Thus, important lessons on the reaction mechanisms and selectivity can be learned. These properties are crucial for experimental researches to design novel transition metal homogeneous catalysis. This chapter presents recent computational studies, employing density functional theory or density functional theory/molecular mechanics methods in cross-coupling and nitrogen reduction reactions. Detailed computational studies rationalized the electronic structure of the transition metal catalysts and the reaction mechanism of the full catalytic cycles. Also, systematic surveys of the selectivity determining transition states of the asymmetric cross-coupling reactions rationalized the origin of the selectivity. Thus, lessons from the computational studies can guide the experimental researchers to develop novel homogeneous catalysis for potential applications in industry or academia.