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- Title
Computational NMR Spectra of o‐Benzyne and Stable Guests and Their Hemicarceplexes.
- Authors
Castro, Abril C.; Romero‐Rivera, Adrian; Osuna, Sílvia; Houk, K. N.; Swart, Marcel
- Abstract
The incarceration of o‐benzyne and 27 other guest molecules within hemicarcerand 1, as reported experimentally by Warmuth, and Cram and co‐workers, has been studied by density functional theory (DFT). The 1H NMR chemical shifts, rotational mobility, and conformational preference of the guests within the supramolecular cage were determined, which showed intriguing correlations of the chemical shifts with structural parameters of the host–guest system. Furthermore, based on the computed chemical shifts reassignments of some NMR signals are proposed. This affects, in particular, the putative characterization of the volatile benzyne molecule inside a hemicarcerand, for which our CCSD(T) and KT2 results indicate that the experimentally observed signals are most likely not resulting from an isolated o‐benzyne within the supramolecular host. Instead, it is shown that the guest reacted with an aromatic ring of the host, and this adduct is responsible for the experimentally observed signals.
- Subjects
CHEMICAL shift (Nuclear magnetic resonance); DENSITY functional theory; HOSPITALITY
- Publication
Chemistry - A European Journal, 2020, Vol 26, Issue 12, p2626
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201904756