Ab initio study of intr amolecular fluorine transfer in perfluoroguanidine

Perfluoroguanidine (CF۵N۳, P FG) a colo rless liquid with molecular weight of ۱۴۹.۰۲ g/mol and b oiling point of ۴۴.۴ °C contains one imino- and two amino- nitrogen at oms bonded to its only c arbon atom, and five fluorine atom s attached to the nitro gen atoms (Fig. ۱). PF G has eight hydrogen-bo nd acceptor and no hyd rogen-bond donor. PF G forms several adducts with alcoho ls which ar e powerful explosives se nsitive to i mpact, fricti on and heat. PFG is use d also as a liquid rocket fuel oxidant. When heated to deco mposition, P FG emits toxic fumes of F۲. Characterization a nd interpretation of th e chemical r eactivity an d physical behavior of PFG are ne cessary for its clever use in the desired appli cations. Computational methods can be consid ered as c ost-effective and the most gr een metho ds for carrying out such charac terization. In this work,thefluorine transfer reaction fr om the amine to the imine nitrogen atom (sigmatropic rearrangement) in the P FG molecu le in the gas phase and the effect of protonation at the im ino and am ino nitroge n sites on this transfer h ave been studied comp utationally. The intrinsic reaction coordinate (IRC) of this intramolecular flu orine transf er in PFG passes through a symmet ric intermediate and resu lts in an identical structure.

کلیدواژه ها:

Perflu oroguanidin e ، Fluorine Transfer ، Proton Transfer ، IRC ، Transition State