Elimination of HF from CH 3F by As + and Bi +: A comparative theoretical study

Abstract

The reactions of ground state As + and Bi + with CH 3F have been investigated at B3LYP and CCSD(T) levels of theory. Two pathways were found for the HF-elimination reactions for both the two atomic ions. The reaction 3As + + CH 3F→ 3AsCH 2 + + HF is exothermic by 72.4 kJ/mol, whereas the reaction 3Bi ++CH 3F→ 3BiCH 2 + + HF is endothermic by 45.7 kJ/mol. The lowest energy pathway for the reaction of As + with CH 3F has activation energy of 70.7 kJ/mol while the corresponding barrier for the reaction of Bi + with CH 3F is much higher (174.6 kJ/mol). The higher reactivity of As + toward CH 3F rationalizes the experimental results of the efficient formation of AsCH 2 + and the absence of BiCH 2 +.