{
  "abstract": "Manganese porphyrins have been widely employed as catalysts for nitrogen-group transfer (NGT) and oxygen-atom transfer (OAT) reactions with olefins and C–H bonds. These transformations are typically proposed to proceed via high-valent manganese nitrenoid and oxo intermediates, respectively. While porphyrin redox non-innocence — in which electron transfer from the ligand to the metal delocalizes high-valent states across the metal and the ancillary ligand — is well established. The potential role of porphyrin chemical non-innocence — in which an atom or group inserts into the M–pyrrolide bond — is much less appreciated. Here, we demonstrate that treatment of Mn(tpp)Cl with iminoiodinanes (PhI═NR, R = Ts (tosyl) and Ns (nosyl)) affords the corresponding tucked-in Mn porphyrins in which the iminoiodinane-derived nitrene fragment has inserted into one of the Mn–N bonds. Nitrene insertion into the Mn–N bond was characterized by NMR, UV-vis, and high-frequency and -field EPR (HFEPR) spectroscopies, as well as single-crystal X-ray diffraction. Nitrene insertion into the Mn–N bond is reversible under both thermal and photochemical conditions; untucking in the presence of styrene affords the corresponding aziridine, demonstrating that the tucked-in porphyrin can function as a latent nitrene equivalent. In situ UV-vis spectroscopy and kinetics experiments of Mn(tpp)Cl-catalyzed styrene aziridination demonstrate that, despite the chemical viability of nitrene insertion / de-insertion reactions, the formation of tuck-in porphyrins is slow relative to olefin aziridination. These results demonstrate that reversible formation of nitrene tuck-in porphyrins is chemically accessible and represents a latent source of electrophilic nitrene equivalents and that in the context of Mncatalyzed aziridination, these elementary steps are slow relative to catalysis.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry",
    "Texas A&M University",
    "Department of Biological and Physical Sciences",
    "Roosevelt University",
    "National High Magnetic Field Laboratory",
    "Florida State University"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Arka Sinha"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Ryan X. Gruen"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Matthew T. Figgins"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Joseph Reibenspies"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Joshua Telser"
    },
    {
      "affs": [
        4,
        5
      ],
      "name": "J. Krzystek"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "David C. Powers",
      "orcid": "0000-0003-3717-2001"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/2h6mjdg55p7pd.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010103/v1",
  "fulltext_url": null,
  "id": "2h6mjdg55p7pd",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010103/v1",
  "language": null,
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Synthesis and Catalytic Reactions"
    ]
  ],
  "openalex": "W7220941986",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010103/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-08",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/2h6mjdg55p7pd.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15010103",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010103/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Synthesis and Catalytic Reactions",
      "subfield": "organic"
    }
  ],
  "title": "Chemical Non-Innocence in Mn Porphyrin-Catalyzed Nitrene Transfer",
  "title_text": "Chemical Non-Innocence in Mn Porphyrin-Catalyzed Nitrene Transfer",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/2h6mjdg55p7pd",
  "venue": "ChemRxiv",
  "versions": []
}