Substituent effects on cyclonona-3,5,7-trienylidenes: a quest for stable carbenes at density functional theory level.

Nine boat-shaped cyclonona-3,5,7-trienylidenes are compared and contrasted with respect to their multiplicity, nucleophilicity, electrophilicity, band gap (Δ EHOMO − LUMO), Natural bond orbital (NBO) atomic charge, force constant, as well as the aptitude for , and through proper isodesmic reactions at B3LYP/AUG-cc-pVTZ and B3LYP/6-311++G**//B3LYP/6-31+G* levels of theory. The nine cyclic carbenes include unsubstituted (1CH2) plus eight α-cyclopropylcyclonona-3,5,7-trienylidenes, which are substituted with ά-SiMe2, ά-NMe, ά-PMe, ά-O, ά-S, ά-CH2, ά-cyclopropyl, and ά-CMe2 (2SiMe2, 2NMe, 2PMe, 2O, 2S, 2CH2, 2cyclopropyl, and 2CMe2, respectively). The latter eight species enjoy the stabilizing interaction of the occupied Walsh orbital of cyclopropyl with the vacant pπ orbital of the carbene center ( Walshcyclopropyl → pπ carbene). Among them, the singlet closed shell 2NMe appears the most promising for exhibiting the highest relative singlet-triplet energy gap (Δ Es − t = 27.1 kcal mol−1). In contrast, the least stable derivative is triplet 2SiMe2, which exhibits the lowest relative Δ Es − t of −5.5 kcal mol−1. The overall trend of Δ Es-t is 2NMe > 2PMe > 2S > 2O > 2cyclopropyl > 2CMe2 > 2CH2 > 1CH2 > 2SiMe2. With one negative force constant, the unsubstituted 1CH2 turns out to be a transition state, whereas the rest emerge as minima. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]