An ab initio and matrix isolation infrared study of the 1:1 C₂H₂-CHCl₃ adduct

Abstract

The details of weak C-H···π interactions that control several inter and intramolecular structures have been studied experimentally and theoretically for the 1:1 C₂H₂-CHCl₃ adduct. The adduct was generated by depositing acetylene and chloroform in an argon matrix and a 1:1 complex of these species was identified using infrared spectroscopy. Formation of the adduct was evidenced by shifts in the vibrational frequencies compared to C₂H₂ and CHCl₃ species. The molecular structure, vibrational frequencies and stabilization energies of the complex were predicted at the MP2/6-311+G(d,p) and B3LYP/6-311+G(d,p) levels. Both the computational and experimental data indicate that the C₂H₂-CHCl₃ complex has a weak hydrogen bond involving a C-H···π interaction, where the C₂H₂ acts as a proton acceptor and the CHCl₃ as the proton donor. In addition, there also appears to be a secondary interaction between one of the chlorine atoms of CHCl₃ and a hydrogen in C₂H₂. The combination of the C-H···π interaction and the secondary Cl···H interaction determines the structure and the energetics of the C₂H₂-CHCl₃ complex. In addition to the vibrational assignments for the C₂H₂-CHCl₃ complex we have also observed and assigned features owing to the proton accepting C₂H₂ submolecule in the acetylene dimer.