{
  "abstract": "We report on the synthesis and characterization of the square planar rhodium(II) alkynyl complex [Rh(PNP-tBu)(C equivalent to CtBu)]+ and its transformation into the vinylidene derivative [Rh(PNP-tBu)(C=CHtBu)]⁺ by reaction with 9,10-dihydroanthracene. Computational analysis supports a mechanism involving carbon-to-metal hydrogen atom transfer followed by 1,3-hydride migration, and intermediate formation of the associated rhodium(III) alkynyl hydride [Rh(PNP-tBu)H(C equivalent to CtBu)]⁺ has been substantiated experimentally. Study of [Rh(PNP-tBu)(C equivalent to CtBu)]+ in the solid state by EPR spectroscopy, supplemented by multireference CAS(9,6)/NEVPT2 calculations, enabled assignment as a metal-centered radical to be corroborated, while analysis of frozen glass solutions revealed the presence of square pyramidal solvent adducts of tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-difluorobenzene, fluorobenzene, and alpha,alpha,alpha-trifluorotoluene. Consistent with a carbon-to-metal hydrogen atom transfer mechanism, the extent of solvent coordination measured by EPR spectroscopy inversely correlates with the rate at which the metalloradical reacts with 9,10-dihydroanthracene.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 9,
  "authors": [
    {
      "name": "Thomas M. Hood"
    },
    {
      "name": "Sophie H. Dewick"
    },
    {
      "name": "John, Anjali"
    },
    {
      "name": "Jeremiah P. Tidey"
    },
    {
      "name": "Julie V. Macpherson"
    },
    {
      "name": "Ragnar Björnsson"
    },
    {
      "name": "Emma Richards"
    },
    {
      "name": "Tobias Krämer"
    },
    {
      "name": "Adrian B. Chaplin"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/c8z79cn1qs11p.bib",
  "cited_by": 2,
  "doi": "10.1021/acs.organomet.6c00053",
  "fulltext_url": null,
  "id": "c8z79cn1qs11p",
  "issns": [
    "0276-7333",
    "1520-6041"
  ],
  "landing_url": "https://hal.science/hal-05591564v1",
  "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": [
    [
      "hal",
      "0.chim"
    ],
    [
      "hal",
      "1.chim.coor"
    ],
    [
      "hal",
      "1.chim.theo"
    ],
    [
      "openalex",
      "1605|Organometallic Complex Synthesis and Catalysis"
    ]
  ],
  "openalex": "W7147367180",
  "pdf_url": "https://hal.science/hal-05591564/document",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-06",
  "publisher": "American Chemical Society",
  "ris": "https://research.draconitic.com/paper/c8z79cn1qs11p.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:49Z",
      "native_id": "hal-05591564",
      "source": "hal",
      "url": "https://hal.science/hal-05591564v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "hal:1.chim.coor",
      "subfield": "inorganic"
    },
    {
      "field": "chemistry",
      "origin": "hal:1.chim.theo",
      "subfield": "theoretical"
    }
  ],
  "title": "Solvent-Dependent Carbon-to-Metal Hydrogen Atom Transfer Reactivity of a Square Planar Rhodium(II) Alkynyl Complex",
  "title_text": "Solvent-Dependent Carbon-to-Metal Hydrogen Atom Transfer Reactivity of a Square Planar Rhodium(II) Alkynyl Complex",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:17:49Z",
  "url": "https://research.draconitic.com/paper/c8z79cn1qs11p",
  "venue": "Organometallics",
  "versions": []
}