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Journal Article

Characterization of a Triplet Vinylidene

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Pantazis,  Dimitrios A.
Research Group Pantazis, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Kutin, Y., Reitz, J., Antoni, P. W., Savitsky, A., Pantazis, D. A., Kasanmascheff, M., et al. (2021). Characterization of a Triplet Vinylidene. Journal of the American Chemical Society, 143(50), 21410-21415. doi:10.1021/jacs.1c11062.


Cite as: https://hdl.handle.net/21.11116/0000-000A-2825-0
Abstract
Singlet vinylidenes (R2C═C:) are proposed as intermediates in a series of organic reactions, and very few have been studied by matrix isolation or gas-phase spectroscopy. Triplet vinylidenes, however, featuring two unpaired electrons at a monosubstituted carbon atom are thus far only predicted as electronically excited-state species and represent an unexplored class of carbon-centered diradicals. We report the photochemical generation and low-temperature EPR/ENDOR characterization of the first ground-state high-spin (triplet) vinylidene. The zero-field splitting parameters (D = 0.377 cm–1 and |E|/D = 0.028) were determined, and the 13C hyperfine coupling tensor was obtained by 13C-ENDOR measurements. Most strikingly, the isotropic 13C hyperfine coupling constant (50 MHz) is far smaller than the characteristic values of triplet carbenes, demonstrating a unique electronic structure which is supported by quantum chemical calculations.