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These compounds, [Zn(\u03ba<jats:sup>2<\/jats:sup>\u20102,6\u2010{Ph<jats:sub>2<\/jats:sub>PNR}<jats:sub>2<\/jats:sub>(NC<jats:sub>5<\/jats:sub>H<jats:sub>3<\/jats:sub>))Br<jats:sub>2<\/jats:sub>] (R=Me, 1; R=H, <jats:bold>2<\/jats:bold>), were shown to be capable of electrocatalytic reduction of CO<jats:sub>2<\/jats:sub> at \u22122.3\u2005V <jats:italic>vs<\/jats:italic>. Fc<jats:sup>+\/0<\/jats:sup> to selectively yield CO in mixed water\/acetonitrile solutions. These complexes also electrocatalytically generate H<jats:sub>2<\/jats:sub> from water in acetonitrile solutions, at the same potential, with Faradaic efficiencies of up to 90\u2009%. DFT computations support a proposed mechanism involving the first reduction of <jats:bold>1<\/jats:bold> or <jats:bold>2<\/jats:bold> occurring at the PN<jats:sup>3<\/jats:sup>P ligand. Furthermore, computational analysis suggested a mechanism involving metal\u2010ligand cooperation of a Lewis acidic Zn(II) and a basic ligand.<\/jats:p>","DOI":"10.1002\/chem.202303147","type":"journal-article","created":{"date-parts":[[2024,1,15]],"date-time":"2024-01-15T11:39:11Z","timestamp":1705318751000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Electrocatalytic Reduction of CO<sub>2<\/sub> and H<sub>2<\/sub>O with Zn(II) Complexes Through Metal\u2010Ligand Cooperation"],"prefix":"10.1002","volume":"30","author":[{"given":"Somayeh","family":"Norouziyanlakvan","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biomolecular Sciences University of Ottawa  10 Marie Curie Ottawa Ontario Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Patrick","family":"Berro","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biomolecular Sciences University of Ottawa  10 Marie Curie Ottawa Ontario Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gyandshwar Kumar","family":"Rao","sequence":"additional","affiliation":[{"name":"Faculty of Science Engineering And Technology Amity University  Haryana India 122413"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bulat","family":"Gabidullin","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biomolecular Sciences University of Ottawa  10 Marie Curie Ottawa Ontario Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1503-2323","authenticated-orcid":false,"given":"Darrin","family":"Richeson","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biomolecular Sciences University of Ottawa  10 Marie Curie Ottawa Ontario Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,3,7]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00391A"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2016.09.005"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b02181"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jphotochemrev.2015.09.001"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00392"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.3390\/catal2040544"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35272A"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2015.03.014"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2ee03309g"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2ee03250c"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar900253e"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2004.11.018"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2010.06.004"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201501002"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00082"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/cs300685q"},{"key":"e_1_2_9_17_1","first-page":"179","volume-title":"Zn in Catalysis. 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