Mechanistic Study and Conceptual Chemical Reactivity Analysis of Hydroboration of Carbon Dioxide Catalyzed by a Manganese(I)-PNP-Pincer Complex.

Designing efficient and selective catalysts for carbon dioxide reduction is an intensive research area in the recent literature on homogeneous catalysis. In this work, we study the catalytic activity of a newly reported Mn(I)-PNP-pincer catalyst with an embedded aromatic ring. First, we systematically examine its capability to yield different products and highlight the importance of ligand aromaticity and steric effects on metal-ligand cooperativity. We then further conceptually probe its reactivity with descriptors from both conceptual density functional theory and an information-theoretic approach, thereby proposing a novel partitioning of the reaction coordinate into three relevant regions. Our results show that the reactivity in these different regions is governed by different properties such as steric effects, electrophilicity/nucleophilicity, or aromaticity. We anticipate that this methodology, with the analytical tools employed in this study, can be generalized and extended to other catalytic systems and find applications in designing better catalysts.