2,6,10-Tris(dialkylamino)trioxatriangulenium Ions. Synthesis, Structure, and Properties of Exceptionally Stable Carbenium Ions

Abstract

A general synthetic route to a novel type of triamino-substituted planar carbenium ions (5) is reported. The synthetic method is based on a facile and selective nucleophilic aromatic substitution on the tris(2,4,6-trimethoxyphenyl)carbenium ion (1) with amines and gives access to a wide variety of more complex amino-substituted carbenium ions. X-ray crystallography shows that the 2,6,10-tris(N-pyrrolidinyl)-4,8,12-trioxatriangulenium ion (5b) is planar and forms segregated stacks of cations and PF6 anions in the solid phase. The stability of the 2,6,10-tris(diethylamino)-4,8,12-trioxatriangulenium ion 5a is expressed as the pKR+ value, which is determined in strongly basic nonaqueous solution on the basis of a new acidity function C_. The pKR+ value of 5a is measured to be 19.7, which is 10 orders of magnitude higher than the values found for the most stable carbenium ions previously reported. Electrochemical reduction of compound 5a leads to rapid dimerization. Two consecutive one-electron oxidations are identified by cyclic voltammetry.