Theoretical investigation for the mediated activation of the C-CN in CH3CN by Zr atom in the gas phase

The insertion reaction of Zr (4d25s2) into the C-CN bond of CH3CN on the triplet and singlet potential energy surfaces (PESs) has been investigated at the density functional theory (DFT) using the hybrid exchange correlation functional B3LYP and B3PW91 level. The overall reaction is calculated to be exothermic by 54.59 kcal/mol. After the nitrile pi-complex, two distinct reaction paths have been found; we have analyzed the crucial activation barriers of the elementary paths 1 and 2 using the activation strain model and the Curtin-Hammett principle (CHP). Crossing points (CPs) between the potential energy surfaces are located, the minimum energy crossing points (MECPs) are obtained using the algorithm in Harvey method and possible spin inversion processes are discussed by means of spin-orbit coupling (SOC) calculations. These theoretical results can act as a guide to further theoretical and experimental researches.

Energy (ΔG≠) diagrams of the reactions of 3M1 → 3M2 and 3M1 → 3I2, with calculated relative Gibbs energies in kcal/mol.Highlights► The CH3CN activation by Zr in the gas phase is a typical two-state reactivity. ► Two pathways are found on two potential energy surfaces. ► We analyzed paths 1 and 2 using the activation strain model and the Curtin-Hammett principle. ► These theoretical results can act as a guide to further theoretical and experimental researches.