A Carbocationic Triarylmethane-Based Porous Covalent Organic Network.

A thermally stable carbocationic covalent organic network (CON), named RIO-70 was prepared from pararosaniline hydrochloride, an inexpensive dye, and triformylphloroglucinol in solvothermal conditions. This nanoporous organic material has shown a specific surface area of 990 m2 g-1 and pore size of 10.3 Å. The material has CO2 uptake of 2.14 mmol g-1 (0.5 bar), 2.7 mmol g-1 (1 bar), and 6.8 mmol g-1 (20 bar), the latter corresponding to 3 CO2 molecules adsorbed per pore per sheet. It is shown to be a semiconductor, with electrical conductivity (σ) of 3.17×10-7  S cm-1 , which increases to 5.26×10-4  S cm-1 upon exposure to I2 vapor. DFT calculations using periodic conditions support the findings.

Revisiting the mechanism for the polar hydrochlorination of alkenes.

Various kinetic studies of the addition of hydrogen halides to alkenes were carried out in the 1930s, 1940s, and 1970s. Since then, there have been theoretical analyses of several aspects of alkene reactivity and regioselectivity during hydrohalogenation. A few works have studied the influence of the hydrogen halide when it is acting as a catalyst (as well as a reactant) under third-order kinetics. However, there has not been any theoretical investigation of the possibility that there is a carbocation intermediate in the contact ion pair. Therefore, we revisited the mechanistic aspects of this reaction at different levels of theory and using IRC (in a gaseous medium) and ONIOM (with an explicit solvent model). We found that (i) there is only one transition state (one energy barrier) for all possible reaction mechanisms in an apolar medium, (ii) there is no carbocation intermediate when a hydrohalogenation reaction is performed in apolar and polar protic media, (iii) hydrochlorination in apolar and polar protic media occurs through an asynchronous concerted mechanism (not through the stepwise mechanism described in undergraduate/graduate literature), and (iv) there are three possible competing mechanisms (with second-, third-, and fourth-order kinetics) in an apolar medium; the mechanism with fourth-order kinetics has the smallest energy barrier, while that with second-order kinetics (a mechanism in which the hydrogen halide does not also act as a catalyst) has the highest energy barrier. Graphical abstract Hydrochlorination of 2,3-dimethylbutene through an asynchronous concerted mechanism.

The catalytic effect of the NH3 base on the chemical events in the caryolene-forming carbocation cascade.

Caryolene formation occur asynchronously in a concerted way through carbocationic rearrangements involving the generation of a secondary or a tertiary carbocation whether the reaction proceeds in the absence or in the presence of NH3 , respectively. Both caryolene formation mechanisms are analyzed within the general framework of the reaction force; the reaction force constant is used to gain insights into the synchronicity of the mechanisms and the reaction electronic flux helps to characterize the electronic activity taking place during the reaction. DFT calculations at the B3LYP/6-31+G(d,p) level show a clear difference in the mechanisms of the base promoted or base free caryolene formation reactions.