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One complex is a mixed\u2010valent [Np\n,Np\n,Np\n] trimer with two bridging \n\u2010oxos and the other is a [Np\n,Np\n] dimer featuring a single \n\u2010oxo. In both complexes the outer Np centers are capped with terminal oxo ligands. Spectroscopic and spectrokinetic studies aimed at elucidating mechanistic details of complex formation in this system show that intermediate multinuclear [Np\n(OAc)]\n species form prior to metal chelation by the ligand; electrolysis experiments demonstrate that production of Np(V) gives rise to asynchronous proton transfer that does not occur otherwise (in the Np(VI) state) as well as condensation with loss of \n and formation of the polynuclear complexes. We attribute the oxo\u2010deficient nature of these products, with respect to conventional actinyl ([AnO\n]\n) species, to the reduction\/condensation reaction sequence of PCET.<\/jats:p>","DOI":"10.1002\/chem.202402963","type":"journal-article","created":{"date-parts":[[2024,12,2]],"date-time":"2024-12-02T13:34:30Z","timestamp":1733146470000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["PCET\u2010Driven Reactivity of Neptunyl(VI) Yields Oxo\u2010Bridged Np(V) and Np(IV) Species"],"prefix":"10.1002","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5149-0132","authenticated-orcid":false,"given":"Emily R.","family":"Mikeska","sequence":"first","affiliation":[{"name":"Chemical Sciences and Engineering Division Argonne National Laboratory  Lemont IL 60439"},{"name":"Department of Chemistry University of Kansas  1567 Irving Hill Road Lawrence KS 66045"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8618-5680","authenticated-orcid":false,"given":"Richard E.","family":"Wilson","sequence":"additional","affiliation":[{"name":"Chemical Sciences and Engineering Division Argonne National Laboratory  Lemont IL 60439"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4172-7460","authenticated-orcid":false,"given":"James D.","family":"Blakemore","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Kansas  1567 Irving Hill Road Lawrence KS 66045"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,1,27]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0500030"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr100085k"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr1001436"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.biochem.78.080207.092132"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c09106"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0905020106"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja203249e"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00245"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar400169p"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.2c00254"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr300212f"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1038\/16231"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1131307"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200704420"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200906127"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2017.03.015"},{"key":"e_1_2_7_17_1","doi-asserted-by":"crossref","unstructured":"M. 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