Captodative Versus Push‐Pull Aromatic Cyclopentadienyl Derivatives

ABSTRACT The problem of whether and how the captodative aromatic systems with the donor and acceptor substituents at the same carbon atom of the C=C bond can be more stable than the π‐conjugated push‐pull counterparts with the two substituents in the vicinal position is analyzed for cyclopentadienyl...

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Bibliographic Details
Published in:International journal of quantum chemistry 2024-10, Vol.124 (19), p.n/a
Main Author: Shainyan, B. A.
Format: Article
Language:English
Subjects:
captodative versus push‐pull aromaticity
cyclopentadienyl derivatives
nuclear independent chemical shifts
solvent effect
structural and energetic criteria
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Summary:ABSTRACT The problem of whether and how the captodative aromatic systems with the donor and acceptor substituents at the same carbon atom of the C=C bond can be more stable than the π‐conjugated push‐pull counterparts with the two substituents in the vicinal position is analyzed for cyclopentadienyl derivatives possessing an aromatic cyclopentadienyl ring. The analysis of electronic, magnetic, and structural criteria of aromaticity showed that among typical organic donors, such as amines NR3, ethers R2O, guanidine (NH2)2C=NH, siloxane O(SiH3)2, silatrane, the captodative isomers [cyclopentadienylium]−C(X+) = CH2 can be more stable than their push‐pull isomeric counterparts [cyclopentadienylium]−—CH=CH—X+. The largest energy difference in favor of the former was found to be ca. 13 kcal/mol for X = NH=C(NH2)2.
ISSN:0020-7608
1097-461X
DOI:10.1002/qua.27490