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Here, we investigate how symmetry remodeling of a urea\u2010based SCS modulates electrocatalytic CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010CO reduction using two atropisomeric iron porphyrins,\n                    <jats:bold>\n                      <jats:italic>\u03b1\u03b2\u03b1\u03b2<\/jats:italic>\n                      \u2010UrFe\n                    <\/jats:bold>\n                    and\n                    <jats:bold>\n                      <jats:italic>\n                        \u03b1\n                        <jats:sub>2<\/jats:sub>\n                        \u03b2\n                        <jats:sub>2<\/jats:sub>\n                      <\/jats:italic>\n                      \u2010UrFe\n                    <\/jats:bold>\n                    , which differ solely in the spatial arrangement of identical hydrogen\u2010bond donor groups. Switching from a face\u2010to\u2010face to an adjacent urea\u2010arms configuration enables unprecedented CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010CO conversion under strictly aprotic conditions, in the absence of Br\u00f8nsted or Lewis acids. Combined electrochemical, spectroscopic, kinetic, and DFT studies reveal that the adjacent positioning of the urea arms weakens the stabilization of the initial [Fe\u2500CO\n                    <jats:sub>2<\/jats:sub>\n                    ] intermediate but creates a more open and dynamically reorganizable SCS that permits insertion of a second CO\n                    <jats:sub>2<\/jats:sub>\n                    molecule as an oxygen\u2010atom acceptor, to yield CO and CO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>2<\/jats:sup>\n                    \u02c9. Under protic conditions, this improved active\u2010site accessibility, combined with a dissymmetrization of the activated CO\n                    <jats:sub>2<\/jats:sub>\n                    molecule, accelerates proton transfer, with CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010CO reduction reaching turnover frequency of up to 2.72\u00a0\u00d7\u00a010\n                    <jats:sup>7<\/jats:sup>\n                    s\n                    <jats:sup>\u22121<\/jats:sup>\n                    , among the highest reported for homogeneous catalysis. These results establish directional interactions within the SCS as powerful design strategy for boosting molecular catalysis.\n                  <\/jats:p>","DOI":"10.1002\/anie.1490828","type":"journal-article","created":{"date-parts":[[2026,7,23]],"date-time":"2026-07-23T10:14:18Z","timestamp":1784801658000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Directional Second Sphere Effect on CO\n                    <sub>2<\/sub>\n                    Activation and Reduction by Iron Porphyrin in Aprotic and Protic Media"],"prefix":"10.1002","volume":"65","author":[{"given":"Ashutosh","family":"Vishwakarma","sequence":"first","affiliation":[{"name":"CNRS Institut De Chimie Mol\u00e9culaire Et Des Mat\u00e9riaux d'Orsay Universit\u00e9 Paris\u2010Saclay  Orsay France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sami","family":"Essid","sequence":"additional","affiliation":[{"name":"CNRS Institut De 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