Toward phenanthridin-2-ylidene: electrophilicity versus acidity in planar-constrained C-aryl iminium salts

Chemistry of Iminium Salts and Related Compounds

Chemistry of Iminium Salts and Related Compounds

Iminium Salts by Meerwein Alkylation of Ehrlich’s Aldehyde

4-(Dimethylamino)benzaldehyde is alkylated at the N atom by dialkyl sulfates, MeI, or Me3O BF4. In contrast, ethylation by Et3O BF4 occurs selectively at the O atom yielding a quinoid iminium ion. 4-(Diethylamino)benzaldehyde is alkylated only at O by either Et or Me oxonium reagent. The iminium salts are prone to hydrolysis giving the corresponding hydrotetrafluoroborates. Five crystal structu...

Chemistry of Iminium Salts, Imines, and Related Compounds

2-Adamantylidene and its heavier analogues: hyperconjugation versus lone pair stability and electrophilicity versus nucleophilicity.

The structure, bonding and reactivity of 2-adamantylidene and its heavier group-14 analogues, 2X (X10H14, X = C-Sn), have been studied at the M06/def2-TZVPP//BP86/def2-TZVPP level of theory. 2-Adamantylidene and its heavier analogues, 2X, have a singlet ground state, where the carbene and silylene bridges in 2C and 2Si are bent similarly to the foiled-type carbenes. The bending of the carbene a...