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Metalloporphyrins and metallophthalocyanines are under high scrutiny since their most classic derivatives the tetraphenylporphyrin (TPP) and parent phthalocyanine (Pc), have been used as the molecular platform to install, hydrogen bonds donors, proton relays, cationic fragments, incorporation in MOFs and COFs, to enhance the catalytic power of these catalysts. Herein, we examine the electrocatalytic properties of the tetramethyl cobalt (II) tetrapyridinoporphyrazine (<jats:bold>CoTmTPyPz<\/jats:bold>) for the reduction of CO<jats:sub>2<\/jats:sub> in heterogeneous medium when adsorbed on carbon nanotubes (CNT) at a carbon paper (CP) electrode. Unlike reported electrocatalysis with cobalt based phthalocyanine where CO was advocated as the two electron and two protons reduced intermediate on the way to the formation of methanol, we found here that <jats:bold>CoTmTPyPz<\/jats:bold> does not reduce CO to methanol. Henceforth, ruling out a mechanistic pathway where CO is a reaction intermediate.<\/jats:p>","DOI":"10.1002\/anie.202411967","type":"journal-article","created":{"date-parts":[[2024,8,1]],"date-time":"2024-08-01T04:48:51Z","timestamp":1722487731000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Cobalt Tetracationic 3,4\u2010Pyridinoporphyrazine for Direct CO<sub>2<\/sub> to Methanol Conversion Escaping the CO Intermediate Pathway"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2176-5953","authenticated-orcid":false,"given":"Chanjuan","family":"Zhang","sequence":"first","affiliation":[{"name":"Universit\u00e9 Paris-Saclay, CNRS Institut de Chimie Mol\u00e9culaire et des Mat\u00e9riaux d'Orsay  91405 Orsay France"},{"name":"Current address: Electrochemical Excellent Center Flemish Institute for Technological Research (VITO)  Boeretang 200 2400 Mol 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