2023
DOI: 10.26434/chemrxiv-2023-l76mw
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Modulating Escape Channels of Cycloheptatrienyl Rhodium Carbenes to Form Semibullvalene

Abstract: We report the various escape channels available to dirhodium carbene intermediates from cycloheptatrienyl diazo compounds with density functional theory. An intramolecular cyclopropanation would, in principle, provide a new route to semibullvalenes. A full exploration of the potential energy surface reveals that methylating carbon-7 suppresses a competing β-hydride migration pathway to heptafulvene products, giving semibullvalene formation a reasonable chance. During our explorations, we additionally discovere… Show more

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