Mechanistic Insight of High-Valent First-Row Transition Metal Complexes for Dehydrogenation of Ammonia Borane

Designing an efficient and cost-effective catalyst for ammonia borane (AB) dehydrogenation remains a persistent challenge in advancing a hydrogen-based economy. Transition metal complexes, known for their C-H bond activation capabilities, have emerged as promising candidates for AB dehydrogenation. In this study, we investigated two recently synthesized C-H activation catalysts, 1 (Co^IV-dinitrate complex) and 2 (Ni^IV-nitrate complex), and demonstrated their efficacy for AB dehydrogenation. Using density functional theory calculations and a detailed analysis, we elucidated the AB dehydrogenation mechanism of these complexes. Our results revealed that both complexes 1 and 2 can efficiently dehydrogenate AB at room temperature, although the abstraction of molecular H₂ from these complexes requires slightly elevated temperatures. We utilized H₂ binding free energy calculations to identify potentially active sites and observed that complex 2 can release two equivalents of H₂ at a temperature slightly higher than room temperature. Furthermore, we investigated AB dehydrogenation kinetics and thermodynamics in iron (Fe)-substituted systems, complexes 3 and 4. Our results showed that the strategic alteration of the central metal atom, replacing Ni in complex 2 with Fe in complex 4, resulted in enhanced kinetics and thermodynamics for AB dehydrogenation in the initial cycle. These results underscore the potential of high-valent first-row transition metal complexes for facilitating AB dehydrogenation at room temperature. Additionally, our study highlights the beneficial impact of incorporating iron into such mononuclear systems, enhancing their catalytic activity.