Zhaoxin Li, Xin-Xin Liu, Xi Wang, Ling-Ya Peng, Chenrui Liu, Zhiqiang Yuan, Yanhong Liu, Ganglong Cui* and Shaowei Hu*,
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Catalytic Silylation of Dinitrogen by PCP-Ligated Chromium Complexes
Despite substantial advances in transition metal-catalyzed N2 silylation, chromium (Cr) catalysts remain scarce and inefficient. We report a PCP-ligated (2,6-(tBu2PCH2)2-C6H3) Cr dinitrogen complex that catalyzes N2 reduction, delivering up to 100.3 equiv of N(SiMe3)3 in 75% yield. Reductive silylation yielded an anionic Cr bis(silyldiazenido) species via functionalization of two N2 ligands. Suppressed activity under high N2 pressure suggests that catalysis proceeds via silylation of a singly N2-bound Cr intermediate. Upon reduction and silylation, a Cr silylamide released N(SiMe3)3 and regenerated the Cr dinitrogen complex, mimicking the final steps of the cycle. The high efficiency arises from both intrinsic reactivity and suppression of side reactions, establishing PCP–Cr scaffolds as powerful platforms for N2 activation.
期刊介绍：
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
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