Additional Reaction and Mechanism of Dicyanobenzene: Formation of Charge-Assisted Hydrogen Bond Networks

Abstract

The interaction of LiN(SiMe 3 ) 2 with one equivalent of 1,3- or 1,4-dicyanobenzene followed by the addition of one equivalent of chlorodiphenylphosphine and oxidation by hydrogen peroxide gave charge-assisted hydrogen bond supramolecular polymeric structure compounds of the general formula [ArC(NH 2 ) 2 ] + [Ph 2 PO 2 ] - (Ar = 3-cyanophenyl for 1 , 4-cyanophenyl for 2 ). These compounds, which are composed of a featured type of synthon, show the typical solid-state and film fluorescence. When the above reactions were carried out with half of an equivalent of 1,3-dicyanobenzene, compound 1 and ammonium diphenylphosphinate were produced; with half of an equivalent of 1,4-dicyanobenzene, compound 3 was obtained. A mechanism for the formation of compounds 1-3 was proposed. Results of DFT calculations suggested that the nucleophilic addition reaction to the second cyano group of the dicyanobenzene was a HOMO-controlled process.