The hydroaminomethylation (HAM) reaction converts alkenes into N-alkylated amines and has been well studied for rhodium- and ruthenium-based catalytic systems. Cobalt-based catalytic systems are able to perform the essential hydroformylation reaction, but are also known to form very active hydrogenation catalysts, therefore we examined such a system for its potential use in the HAM reaction. Thus, we have quantum-chemically explored the hydrogenation activity of [HCo(CO)3] in model reactions with ethene, methyleneamine, formaldehyde, and vinylamine using dispersion-corrected relativistic density functional theory at ZORA-BLYP-D3(BJ)/TZ2P. Our computations reveal essentially identical overall barriers for the catalytic hydrogenation of ethene, formaldehyde, and vinylamine. This strongly suggests that a cobalt-based catalytic system will lack hydrogenation selectivity in experimental HAM reactions. Our HAM experiments with a cobalt-based catalytic system (consisting of Co2(CO)8 as cobalt source and P(n-Bu)3 as ligand) resulted in the formation of the desired N-alkylated amine. However, significant amounts of hydrogenated starting material as well as alcohol (hydrogenated aldehyde) were always formed. The use of cobalt-based catalysts in the HAM reaction to selectively form N-alkylated amines seems therefore not feasible. This confirms our computational prediction and highlights the usefulness of state-of-the-art DFT computations for guiding future experiments.
- Density functional calculations
- Homogeneous catalysis
- Reaction mechanisms