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Herein, we synthesized capsule-like cobalt\u2013polypyridine diamine complexes [Co(L1)](BF4)2 (1) and [Co(L2) (CH3CN)](BF4)2 (2) as catalysts for the electrocatalytic reduction of CO2. Under catalytic conditions, complexes 1 and 2 demonstrated the electrocatalytic reduction of CO2 to CO in the presence or absence of CH3OH as a proton source. Experimental and computational studies revealed that complexes 1 and 2 undergo two consecutive reversible one-electron reductions on the cobalt core, followed by the addition of CO2 to form a metallocarboxylate intermediate [CoII(L)\u2013CO22\u2212]0. This crucial reaction intermediate, which governs the catalytic cycle, was successfully detected using high resolution mass spectrometry (HRMS). In situ Fourier-transform infrared spectrometer (FTIR) analysis showed that methanol can enhance the rate of carbon\u2013oxygen bond cleavage of the metallocarboxylate intermediate. DFT studies on [CoII(L)\u2013CO22\u2212]0 have suggested that the doubly reduced species attacks CO2 on the C atom through the dz2 orbital, while the interaction with CO2 is further stabilized by the \u03c0 interaction between the metal dxz or dxz orbital with p orbitals on the O atoms. Further reductions generate a metal carbonyl intermediate [CoI(L)\u2013CO]+, which ultimately releases CO.<\/jats:p>","DOI":"10.3390\/molecules29081694","type":"journal-article","created":{"date-parts":[[2024,4,9]],"date-time":"2024-04-09T08:55:12Z","timestamp":1712652912000},"page":"1694","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Electrocatalytic Reduction of CO2 to CO by Molecular Cobalt\u2013Polypyridine Diamine Complexes"],"prefix":"10.3390","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8623-0453","authenticated-orcid":false,"given":"Yong","family":"Yang","sequence":"first","affiliation":[{"name":"School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fang","family":"Xie","sequence":"additional","affiliation":[{"name":"School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiahui","family":"Chen","sequence":"additional","affiliation":[{"name":"School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Si","family":"Qiu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0006-8491-6682","authenticated-orcid":false,"given":"Na","family":"Qiang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ming","family":"Lu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhongli","family":"Peng","sequence":"additional","affiliation":[{"name":"School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jing","family":"Yang","sequence":"additional","affiliation":[{"name":"College of Health Science and Environmental Engineering, Shenzhen Technology University, Shenzhen 518118, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guocong","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2024,4,9]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1330","DOI":"10.1126\/science.1188566","article-title":"Future CO2 Emissions and Climate Change from Existing Energy Infrastructure","volume":"329","author":"Davis","year":"2010","journal-title":"Science"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"2571","DOI":"10.1016\/j.chempr.2018.08.019","article-title":"Progress toward Commercial Application of Electrochemical Carbon Dioxide Reduction","volume":"4","author":"Chen","year":"2018","journal-title":"Chem"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"89","DOI":"10.1039\/B804323J","article-title":"Electrocatalytic and Homogeneous Approaches to conversion of CO2 to Liquid Fuels","volume":"38","author":"Benson","year":"2009","journal-title":"Chem. 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