{
  "abstract": "Realizing the full potential of actinide-based systems requires strategies to differentiate elements whose similar chemical properties complicate their selective use. Redox-active ligands offer a promising approach: their ability to participate in electron transfer provides a means to tune the oxidation states and electronic structures of both lanthanides and actinides. To explore this approach, we conducted a theory-guided study of (Tp*)2An(dtbsq) complexes (1-An; An = U, Np, Pu, Am, Bk; Tp* = [HB(C3N2Me2H)3]-; dtbsq•− = [C6O2 tBu2H2]-), which contain a redox-active semiquinone ligand. This study reveals a shift in the preferred actinide oxidation state from An(IV) to An(III) between the chemically similar elements Np and Pu. Such an effect is made possible due to differential stabilization of oxidation states by the ligated redox-active ligand. Structural and spectroscopic data are consistent with this trend, as exemplified by the experimentally characterized complexes 2-U ([(Tp*)(Bp*)UIV 2(dtbc)3], Bp* = [H2B(C3N2Me2H)2]-, dtbc = [C6O2 tBu2H2]2-) and 1-Pu [(Tp*)2PuIII(dtbsq)]. In these systems, the radical ligand is reduced to a catecholate only in the presence of UIII but it remains in its radical form with PuIII. Electronicstructure calculations for (Tp*)2An(dtbsq) (An = U, Np, Pu, Am, Bk) reveal tunable AnIII/IV oxidation states—supported by highly multiconfigurational ground states—and oxidation-statedependent covalency. This study advances our fundamental understanding of actinide bonding and highlights oxidation-state control as a promising strategy for tuning reactivity and selectivity across f-block chemistry.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry",
    "University of California, Berkeley",
    "Chemical Sciences Division",
    "Lawrence Berkeley National Laboratory",
    "Theoretical Division",
    "Los Alamos National Laboratory"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "affs": [
        0,
        1,
        2,
        3,
        4,
        5
      ],
      "name": "David J. Fiszbein",
      "orcid": "0000-0001-9005-8035"
    },
    {
      "affs": [
        4,
        5
      ],
      "name": "Maria J. Beltran-Leiva"
    },
    {
      "affs": [
        0,
        1,
        2,
        3
      ],
      "name": "Mikaela M. Pyrch"
    },
    {
      "affs": [
        4,
        5
      ],
      "name": "Enrique R. Batista"
    },
    {
      "affs": [
        0,
        1,
        2,
        3
      ],
      "name": "Polly L. Arnold"
    },
    {
      "affs": [
        4,
        5
      ],
      "name": "Ping Yang"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/58ffncd9mvys8.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010136/v1",
  "fulltext_url": null,
  "id": "58ffncd9mvys8",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010136/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1604|Radioactive element chemistry and processing"
    ]
  ],
  "openalex": "W7221095775",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010136/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-09",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/58ffncd9mvys8.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15010136",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010136/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Radioactive element chemistry and processing",
      "subfield": "inorganic"
    }
  ],
  "title": "A Redox-Non-Innocent Catecholate Shifts the Oxidation State Break in the Actinides",
  "title_text": "A Redox-Non-Innocent Catecholate Shifts the Oxidation State Break in the Actinides",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/58ffncd9mvys8",
  "venue": "ChemRxiv",
  "versions": []
}