In Silico investigation of substitution mechanism at the Nickel carbonyl complex

Abstract

The reaction mechanism of carbon monoxide substitution at the tetracarbonyl nickel complex was studied in depth by DFT calculations. Substituents used in these reactions were hydrogen cyanide, pyridine, trimethylamine, trimethylphosphine, triphenylphosphane, and trimethylarsine, as well as carbon monoxide for the carbon monoxide exchange reaction. To investigate the reaction mechanism, reaction energy, reaction force, and reaction force constant profile were calculated. Additionally, changes of electron density at bond critical points of a breaking and a forming bond were monitored along the reaction. All gathered data were further statistically analyzed in order to find a possible correlation between them. Results gained in this way point out details that could not be observed by conventional experimental investigations of reaction kinetics and mechanisms but certainly should be taken into account in further designing of suitable complexes for desirable reactions.