Tuning the nucleophilicity in cyclopropenylidenes

Schoeller W, Frey GD, Bertrand G (2008)
CHEMISTRY-A EUROPEAN JOURNAL 14(15): 4711-4718.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
Cyclopropenylidenes are Huckel aromatic pi systems in which one of the ring atoms is a carbene center. Quantum chemical calculations at the density functional level of theory, supplemented by coupled-cluster calculations, indicate that there is a sizeable energy separation between the lowest-energy singlet and triplet states of these species. Amino groups considerably increase the energy difference between these two states, whereas electron-withdrawing substituents decrease it. The 1,1-dimerization products of cyclopropenylidenes, namely, triafulvalenes, have been investigated. The calculations show that, without steric hindrance and considerable electronic stabilization, cyclopropenylidenes are kinetically unstable and dimerize. Different substituents (alkyl, sityl, terphenyl, amino, and phosphoraneiminato) were probed to tune the frontier orbital energies of cyclopropenylidenes. Accordingly, it is predicted that by a suitable choice of substituents at the olefinic positions, cyclopropenylidenes can be more nucleophilic than their five-membered ring congeners, namely, imidazol-2-ylidenes.
Stichworte
cyclopropenylidenes; singlet-triplet; energy separation; substituent effects; density functional calculations; triafulvalenes
Erscheinungsjahr
2008
Zeitschriftentitel
CHEMISTRY-A EUROPEAN JOURNAL
Band
14
Ausgabe
15
Seite(n)
4711-4718
ISSN
0947-6539
eISSN
1521-3765
Page URI
https://pub.uni-bielefeld.de/record/1587702

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Schoeller W, Frey GD, Bertrand G. Tuning the nucleophilicity in cyclopropenylidenes. CHEMISTRY-A EUROPEAN JOURNAL. 2008;14(15):4711-4718.
Schoeller, W., Frey, G. D., & Bertrand, G. (2008). Tuning the nucleophilicity in cyclopropenylidenes. CHEMISTRY-A EUROPEAN JOURNAL, 14(15), 4711-4718. doi:10.1002/chem.200701926
Schoeller, W., Frey, G. D., and Bertrand, G. (2008). Tuning the nucleophilicity in cyclopropenylidenes. CHEMISTRY-A EUROPEAN JOURNAL 14, 4711-4718.
Schoeller, W., Frey, G.D., & Bertrand, G., 2008. Tuning the nucleophilicity in cyclopropenylidenes. CHEMISTRY-A EUROPEAN JOURNAL, 14(15), p 4711-4718.
W. Schoeller, G.D. Frey, and G. Bertrand, “Tuning the nucleophilicity in cyclopropenylidenes”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 14, 2008, pp. 4711-4718.
Schoeller, W., Frey, G.D., Bertrand, G.: Tuning the nucleophilicity in cyclopropenylidenes. CHEMISTRY-A EUROPEAN JOURNAL. 14, 4711-4718 (2008).
Schoeller, Wolfgang, Frey, Guido D., and Bertrand, Guy. “Tuning the nucleophilicity in cyclopropenylidenes”. CHEMISTRY-A EUROPEAN JOURNAL 14.15 (2008): 4711-4718.

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