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 ( POCN )Ni(CH 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 ( POCN )Ni(CH CN) that is reported to accomplish the cyanomethylation at room temperature. While pincer complexes ( NNN)Ni(CH CN) and ( NCN)Ni(CH CN) containing strong σ-donating amines were found to fare poorly, pincer-nickel complexes ( NCN)Ni(CH CN) and ( PheboxNCN)Ni(CH CN) based on weaker σ-donating imines had energetics more favorable than the reported efficient catalyst ( POCN )Ni(CH 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.
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