{
  "abstract": "Ammonia oxidation remains a kinetic bottleneck in utilizing ammonia as a carbon-free energy carrier. Iron-based complexes offer a cost-effective alternative to noble-metal catalysts, but use is hampered by low turnover numbers. Here, density functional theory is used to investigate the catalytic activity and deactivation pathways of Fe2+/Fe3+ complexes bearing cis-ammonia ligands. We confirm the ground-state electronic structures of these complexes, then establish an accurate SMD/DRACO protocolusing a van der Waals cavity with Gaussian-smeared surface charge discretizationthat predicts redox potentials with mean error below 0.013 V versus experiment. Thermodynamic evaluation of sequential hydrogen atom transfer (HAT) steps reveals a “peaked” bond dissociation free energy profile. Crucially, the exergonic third HAT step yields not the anticipated nitrido species, but a novel isomer in which the nitride inserts into the Fe–C bond. This Fe–N–C isomer is a deep thermodynamic sink, trapping the catalyst in an inactive state. A similarly low-energy Fe–N–C isomer exists for the imido intermediate but is kinetically inaccessible. These results indicate that Fe–C-containing complexes are unlikely to serve as efficient AO catalysts, as a high-valent iron center with a multiply bonded nitrogen ligand renders the Fe–C bond prone to alkyl migration, a facile deactivation pathway.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Inorganic and Analytical Chemistry, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem Rkp. 3, Budapest 1111, Hungary"
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Luo Sheng"
    },
    {
      "affs": [
        0
      ],
      "name": "Julianna Oláh",
      "orcid": "0000-0003-4608-3115"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/cw3xgw8w2fejg.bib",
  "cited_by": 0,
  "doi": "10.1021/acs.inorgchem.6c02749",
  "fulltext_url": "https://pmc.ncbi.nlm.nih.gov/articles/PMC13715577/",
  "id": "cw3xgw8w2fejg",
  "issns": [
    "0020-1669",
    "1520-510X"
  ],
  "landing_url": "https://doi.org/10.1021/acs.inorgchem.6c02749",
  "language": "en",
  "licence": "CC-BY-4.0",
  "licence_label": "CC BY 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Article"
    ],
    [
      "openalex",
      "1605|Organometallic Complex Synthesis and Catalysis"
    ]
  ],
  "openalex": "W7221705076",
  "pdf_url": "https://pubs.acs.org/inocaj/article-pdf/doi/10.1021/acs.inorgchem.6c02749/68842403/acs.inorgchem.6c02749.pdf",
  "pmcid": "PMC13715577",
  "pmid": "42929630",
  "published": "2026-10-13",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/cw3xgw8w2fejg.ris",
  "sources": [
    {
      "first_seen": "2026-11-01T12:22:51Z",
      "native_id": "PMC13715577",
      "source": "pmc",
      "url": "https://doi.org/10.1021/acs.inorgchem.6c02749"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Organometallic Complex Synthesis and Catalysis",
      "subfield": "organic"
    }
  ],
  "title": "Iron–Nitride Isomerization as a Deactivation Pathway in Ammonia Oxidation: A Computational Study of Sequential HAT Mechanisms",
  "title_text": "Iron–Nitride Isomerization as a Deactivation Pathway in Ammonia Oxidation: A Computational Study of Sequential HAT Mechanisms",
  "type": "peer-reviewed",
  "updated_at": "2026-11-01T12:22:51Z",
  "url": "https://research.draconitic.com/paper/cw3xgw8w2fejg",
  "venue": "Inorganic Chemistry",
  "versions": []
}