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Since the experimental results were inconclusive regarding the influence of the uranyl\u2010bound tetra\u2010dentate \u2018salmnt\u2019 ligand, here we will show that salmnt acts as a redox\u2010active ligand and exhibits non\u2010innocent behavior to interfere with the otherwise expected one\u2010electron metal (U) reduction. We have employed two approaches to determine the uranyl (VI\/V) reduction potentials, using a direct study of one\u2010electron reduction processes and an estimation of the overall reduction using isodesmic reactions. Hybrid density functional theory (DFT) methods were combined with the Conductor\u2010like Polarizable Continuum Model (CPCM) to account for solvation effects. The computationally predicted one\u2010electron reduction potentials for the range of [UO<jats:sub>2<\/jats:sub>\u2010salmnt\u2010L] complexes are in excellent agreement with shoulder peaks (\u223c1.4\u2005eV) observed in the cyclic voltammetry experiments and clearly correlate with ligand reduction. Highly conjugated pi\u2010bonds stabilize the ligand based delocalized orbital relative to the localized U f\u2010orbitals, and as a consequence, the ligand traps the incoming electron. A second reduction step results in metal U(VI) to U(V) reduction, in good agreement with the experimentally assigned uranyl (VI\/V) reduction potentials.<\/jats:p>","DOI":"10.1002\/cphc.201900301","type":"journal-article","created":{"date-parts":[[2019,5,7]],"date-time":"2019-05-07T08:35:18Z","timestamp":1557218118000},"page":"1869-1878","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Uranyl\u2010Bound Tetra\u2010Dentate Non\u2010Innocent Ligands: Prediction of Structure and Redox Behaviour Using Density Functional Theory"],"prefix":"10.1002","volume":"20","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8638-9739","authenticated-orcid":false,"given":"Krishnamoorthy","family":"Arumugam","sequence":"first","affiliation":[{"name":"School of Chemistry The University of Manchester  Oxford Road Manchester United Kingdom"},{"name":"Current address: National Post Doctoral Fellow (NPDF) Simulation Center for Atomic and Nanoscale Materials (SCANMAT) Central University of Tamil Nadu  Thiruvarur, Tamil Nadu- 610101 India'"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5773-3844","authenticated-orcid":false,"given":"Neil A.","family":"Burton","sequence":"additional","affiliation":[{"name":"School of Chemistry The University of Manchester  Oxford Road Manchester United Kingdom"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2019,6,17]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1007\/BFb0036502"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic0201708"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr300198m"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1515\/REVIC.1995.15.1-2.1"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(00)95588-9"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4812360"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic5006314"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic8010772"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp063060l"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1038\/srep32898"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4DT02112F"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic201881k"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/B607144A"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201101359"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35228A"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1070\/RCR4837"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.5b06370"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic700781t"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.crci.2010.04.011"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.5b00467"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja1089364"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7DT01993A"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CP05412F"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b11302"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6SC02912D"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.organomet.7b00454"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6DT02089E"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3dt50698c"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.7b01560"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0dt01580f"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic901487r"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic9814423"},{"key":"e_1_2_7_33_1","unstructured":"K. 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