Pentacycloundecanylidene and pentacycloundecanone – hyperconjugatively stabilized carbene and ketone

Abstract

Pentacycloundecanylidene was spectroscopically identified during the photolysis of the corresponding aziridine and its aerial oxidation results in the corresponding ketone. Here we report the role of hyperconjugative interactions in stabilizing the singlet pentacycloundecanylidene and its corresponding ketone pentacycloundecanone. The pentacycloundecanylidene possesses a singlet ground state with two possible geometrical isomers based on the orientation of the carbene bridge (U1 and U2). The energy difference between U1 and U2 is minimal (0.9 kcal mol⁻¹) and the triplet state is 5.6 kcal mol⁻¹ energetically higher than the more stable singlet state U1. The proximal C–C bonds of the carbene bridge in the singlet state are significantly elongated as compared to the distal C–C bonds. The bending of the carbene bridge in the triplet state and the carbonyl group in the ketone are minimal as compared to the parent pentacycloundecane. The molecular orbital (MO), natural bond orbital (NBO) and energy decomposition analysis (EDA) show that both Cieplak-type hyperconjugation viz. donation of electrons from the proximal C–C σ bonds to the empty p-orbital on the carbene centre and Felkin–Anh type hyperconjugation viz. donation of the lone pair of carbene carbon to the distal C–C σ* orbitals exist in carbene systems. The bending of the carbene bridge in singlet carbene is to enhance the Cieplak-type hyperconjugative interaction. The ketone is also stabilized by Cieplak-type hyperconjugative interaction but to a lower extent as compared to the singlet carbene. The reactivity study suggests that the singlet pentacycloundecanylidene is ambiphilic in nature.