Theoretical study of the Ru + CH₃F reaction

Abstract

CASSCF-MRMP2 calculations have been performed to analyse the reaction of fluoromethane with a bare ruthenium atom. Potential energy curves emerging from the ground state and the first excited state of the reactants, Ru(⁵F, ³F;d⁷s¹) + CH₃F, were calculated for representative electronic states associated with different approaching modes of the fragments. Whereas no favourable channels correlating with the ground state asymptote were detected for the insertion of the ruthenium atom into the C–H bond of the methyl fluoride molecule, the oxidative addition of the C–F bond of this molecule to the metal atom along the reaction path evolving from the ground state of the fragments leads to the stable inserted product CH₃–Ru–F. Although forming less stable products, insertion of ruthenium into the C–H and C–F bonds of the fluorocarbon molecule can occur through electronic states which emerge from the excited triplet state asymptote.

Keywords:

• C–F activation
• ruthenium
• potential energy curves

Acknowledgements

This research was partially supported by the Universidad Nacional Autónoma de México (DGAPA-IN105007) and El Consejo Nacional de Ciencia y Tecnología (CONACYT-52309).