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Divanadium(III) complexes with four symmetric pyramidal bridging methyl or parent amido ligands, [{VCp*(\u00b5\u2010X)\n                    <jats:sub>2<\/jats:sub>\n                    }\n                    <jats:sub>2<\/jats:sub>\n                    ] (Cp* = \u03b7\n                    <jats:sup>5<\/jats:sup>\n                    \u2010C\n                    <jats:sub>5<\/jats:sub>\n                    Me\n                    <jats:sub>5<\/jats:sub>\n                    , X = CH\n                    <jats:sub>3<\/jats:sub>\n                    , NH\n                    <jats:sub>2<\/jats:sub>\n                    ), exhibit an open\u2010shell singlet ground state with a single V\u2500V bond and a relatively small singlet\u2012triplet energy gap, according to theoretical calculations and magnetic measurements. The thermal decomposition of the tetramethyl species in hexane at 160\u00b0C cleanly affords the tetranuclear cube\u2010type methylidene complex [{VCp*(\u00b5\n                    <jats:sub>3<\/jats:sub>\n                    \u2010CH\n                    <jats:sub>2<\/jats:sub>\n                    )}\n                    <jats:sub>4<\/jats:sub>\n                    ] with the release of methane. In contrast, the analogous thermolysis in benzene or toluene allows the isolation of trovacene derivatives with \u03b7\n                    <jats:sup>7<\/jats:sup>\n                    \u2010cycloheptatrienyl ligands [VCp*(\u03b7\n                    <jats:sup>7<\/jats:sup>\n                    \u2010C\n                    <jats:sub>7<\/jats:sub>\n                    H\n                    <jats:sub>6<\/jats:sub>\n                    R)] (R = H, Me), via a formal insertion of a CH fragment into the six\u2010membered aromatic ring of the solvent. A similar ring expansion is observed in the thermolysis of the tetramethyl compound in naphthalene (C\n                    <jats:sub>10<\/jats:sub>\n                    H\n                    <jats:sub>8<\/jats:sub>\n                    ) solution, yielding a trovacene derivative [VCp*(\u03b7\n                    <jats:sup>7<\/jats:sup>\n                    \u2010C\n                    <jats:sub>11<\/jats:sub>\n                    H\n                    <jats:sub>9<\/jats:sub>\n                    )] with the slipped triple\u2010decker sandwich vanadium(I) species [(VCp*)\n                    <jats:sub>2<\/jats:sub>\n                    (\u00b5\u2010\u03b7\n                    <jats:sup>6<\/jats:sup>\n                    :\u03b7\n                    <jats:sup>6<\/jats:sup>\n                    \u2010C\n                    <jats:sub>10<\/jats:sub>\n                    H\n                    <jats:sub>8<\/jats:sub>\n                    )] as an isolated byproduct. Overall, the thermal decomposition of [{VCp*(\u00b5\u2010CH\n                    <jats:sub>3<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    }\n                    <jats:sub>2<\/jats:sub>\n                    ] in benzenic solvents leads to variable mixtures of methylidene [{VCp*(\u00b5\n                    <jats:sub>3<\/jats:sub>\n                    \u2010CH\n                    <jats:sub>2<\/jats:sub>\n                    )}\n                    <jats:sub>4<\/jats:sub>\n                    ] and trovacene complexes depending on arene substituents.\n                  <\/jats:p>","DOI":"10.1002\/chem.202502798","type":"journal-article","created":{"date-parts":[[2026,3,11]],"date-time":"2026-03-11T13:25:20Z","timestamp":1773235520000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Arene Incorporation and Ring Expansion in the Thermal Decomposition of a Divanadium(III) Complex With Four Bridging Methyl Groups"],"prefix":"10.1002","volume":"32","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1634-680X","authenticated-orcid":false,"given":"Adri\u00e1n","family":"Calvo\u2010Molina","sequence":"first","affiliation":[{"name":"Departamento de Qu\u00edmica Org\u00e1nica y Qu\u00edmica Inorg\u00e1nica Instituto de Investigaci\u00f3n Qu\u00edmica \u201cAndr\u00e9s M. del R\u00edo\u201d (IQAR) Universidad de Alcal\u00e1  Alcal\u00e1 de Henares\u2010Madrid Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9445-9901","authenticated-orcid":false,"given":"Rodrigo","family":"Gonz\u00e1lez\u2010Prieto","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Facultad de Ciencias Qu\u00edmicas Universidad Complutense de Madrid  Madrid 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