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.
Authors
- Ling‐Ya Peng (ORCID: https://orcid.org/0000-0002-0589-3253)
- Ganglong Cui (ORCID: https://orcid.org/0000-0002-9752-1659)
- Shaowei Hu (ORCID: https://orcid.org/0000-0002-7209-438X)
- Xinxin Liu (ORCID: https://orcid.org/0000-0003-3722-9020)
- Xi Wang (ORCID: https://orcid.org/0000-0003-3910-9575)
- Yanhong Liu (ORCID: https://orcid.org/0000-0003-0749-2602)
- Laurent Li (ORCID: https://orcid.org/0000-0002-3855-3976)
- Chenrui Liu (ORCID: https://orcid.org/0009-0004-0294-5128)
- Zhong Yuan
Institutions
- Beijing Normal University (CN)
- Technical Institute of Physics and Chemistry (CN)
- Shaanxi Normal University (CN)
Publication Details
- Journal
- ACS Catalysis
- Published
- 2025-07-18
- DOI
- https://doi.org/10.1021/acscatal.5c03731
- Citations
- 7
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 6.55
Funders
- National Natural Science Foundation of China
- Scientific Research Foundation of Beijing Normal University
- Fundamental Research Funds for the Central Universities
- Thousand Young Talents Program of China