The electronic donation and frequency shifts on the YCCH⋯BH4− boron-bonded complexes (Y = H, CH3, CF3 and CCl3)

Abstract

In this theoretical work, the tetrahydroborate ion (BH4−) was used as proton acceptor in the formation of the YCC–H⋯BH4− complexes (Y=H, CH3, CCl3 and CF3). Using B3LYP/6-311++G(d,p) level of theory, the results of structure corroborate with the analyses of infrared spectra showing that the changes in the bond lengths are in good agreement with the frequency shifts of the HCC–H, H3CCC–H, Cl3CCC–H and F3CCC–H proton donors. Based on the calculations carried out by the Quantum Theory of Atoms in Molecules (QTAIM), the reductions of electronic density corroborate with the red shifts in the frequencies of the C–H bonds. In addition to that, the C–H bonds are polarized because the contributions of s orbital diminish whereas of p increase. In line with this, the variations on the atomic radii computed via QTAIM calculations show that carbon outweigh hydrogen as follows (ΔrC>ΔrH). This scenario is indirectly supported by the Bent’s rule of the chemical bonding. Although the interaction energies (corrected with BSSE and ZPE) vary between −19 and −67kJmol−1, these complexes interact without covalent character.