Rational design of pincer-nickel complexes for catalytic cyanomethylation of benzaldehyde: A systematic DFT study

The current study dwells upon the efforts to computationally probe a phosphine-free pincer-nickel complex that would demonstrate an efficiency better than the reported phosphine-based pincer-nickel complex (^iPr2 POCN^Et2 )Ni(CH₂ CN) for cyanomethylation reaction. For this purpose, the mechanism of cyanomethylation of benzaldehyde was studied quantum mechanically for a series of 11 pincer-nickel complexes. The energetics of various intermediates and transition states involved in the catalytic cycle for each catalyst was compared with the corresponding energetics of the Miller's catalyst (^iPr2 POCN^Et2 )Ni(CH₂ CN) that is reported to accomplish the cyanomethylation at room temperature. While pincer complexes (^iPr4 NNN)Ni(CH₂ CN) and (^iPr4 NCN)Ni(CH₂ CN) containing strong σ-donating amines were found to fare poorly, pincer-nickel complexes (^iPr2 NCN)Ni(CH₂ CN) and (^dm PheboxNCN)Ni(CH₂ CN) based on weaker σ-donating imines had energetics more favorable than the reported efficient catalyst (^iPr2 POCN^Et2 )Ni(CH₂ CN). While strong trans-influencing C as the pincer central atom was found to be pivotal for lowering the cyanomethylation kinetics, presence of a poor trans-influencing N proved to be detrimental on the overall energetics.