Synthesis and properties of hypervalent electron-rich pentacoordinate nitrogen compounds.

Isolation and structural characterization of hypervalent electron-rich pentacoordinate nitrogen species have not been achieved despite continuous attempts for over a century. Herein we report the first synthesis and isolation of air stable hypervalent electron-rich pentacoordinate nitrogen cationic radical () species from oxidation of their corresponding neutral () species. In the cationic radical species, the nitrogen centers adopt a trigonal bipyramidal geometry featuring a 3-center-5-electron hypervalent attractive interaction.

Imidazole-stabilized, electron-deficient boron cations.

The borenium cations [(CHNAd)B(CF)][AlCl/AlCl] 2a, and [(CHNMe)B(CF)][B(CF)] 2b were prepared and are shown to feature a high Lewis acidity, the capability to activate hydrogen and to effect the 1,1-carborations of terminal and internal alkynes under mild conditions.