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Effects of ancillary ligands in acceptorless benzyl alcohol dehydrogenation mediated by phosphine-free cobalt complexes |
Yan Xu1, Lu Wang1,3, Junwei Wu1, Guanzhong Zhai1, Daohua Sun1,2() |
1. Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China 2. Department of Chemical and Biochemical Engineering, National Engineering Laboratory for Green Chemical Productions of Alcohols−Ethers−Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China 3. Luoyang Ship Material Institute, Luoyang 471039, China |
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Abstract Acceptorless alcohol dehydrogenation stands out as one of the most promising strategies in hydrogen storage technologies. Among various catalytic systems for this reaction, cost-effective molecular catalysts using phosphine-free ligands have gained considerable attention. However, the central challenge for using non-precious metals is to overcome the propensity of reacting by one-electron pathway. Herein, we synthesized a phosphine-free η5-C5Me5-Co complex by using the metal–ligand cooperative strategy and compared its activity with analogous catalysts toward acceptorless alcohol dehydrogenation. The catalyst showed excellent performance with a turnover number of 130.4 and a selectivity close to 100%. The improved performance among the class of η5-C5Me5-Co complexes could be attributed to the more accessible Co center and its cooperation with the redox-active ligand. To further study the systematic structure-activity relationship, we investigated the electronic structures of η5-C5Me5-Co complexes by a set of characterizations. The results showed that the redox-active ligand has a significant influence on the η5-C5Me5-Co moiety. In the meantime, the proximal O−/OH group is beneficial for shuttling protons. For the catalytic cycle, two dehydrogenation scenarios were interrogated through density functional theory, and the result suggested that the outer-sphere pathway was preferred. The formation of a dihydrogen complex was the rate-determining step with a ΔG value of 16.9 kcal∙mol‒1. The electron population demonstrated that the η5-C5Me5 ligand played a key role in stabilizing transition states during dehydrogenation steps. This work identified the roles of vital ligand components to boost catalytic performance and offered rationales for designing metal–ligand cooperative nonprecious metal complexes.
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Keywords
acceptorless alcohol dehydrogenation
η5-C5Me5-Co
metal–ligand cooperation
theoretical calculation
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Corresponding Author(s):
Daohua Sun
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Online First Date: 15 December 2022
Issue Date: 17 March 2023
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