Role of ancillary ligands in selectivity towards acceptorless dehydrogenation versus dehydrogenative coupling of alcohols and amines catalyzed by cationic ruthenium(II)-CNC pincer complexes.

An unexpected reversal in catalytic activity for acceptorless dehydrogenative coupling compared to acceptorless alcohol dehydrogenation has been observed using a series of cationic Ru(II)-CNC pincer complexes with different ancillary ligands. In continuation of our study of cationic Ru(II)-CNC pincer complexes 1a-6a, new complexes with bulky N-wingtips [Ru(CNCiPr)(CO)(PPh3)Br]PF6 (1b), [Ru(CNCCy)(CO)(PPh3)Cl]PF6 (1c), [Ru(CNCCy)(CO)(PPh3)H]PF6 (2c), [Ru(CNCiPr)(PPh3)2Cl]PF6 (3b), [Ru(CNCCy)(PPh3)2Cl]PF6 (3c), [Ru(CNCiPr)(PPh3)2H]PF6 (4b), [Ru(CNCCy)(PPh3)2H]PF6 (4c), [Ru(CNCiPr)(DMSO)2Cl]PF6 (6b), and [Ru(CNCCy)(DMSO)2Cl]PF6 (6c) [CNCR = 2,6-bis(1-alkylimidazol-2-ylidene)-pyridine] have been synthesized and the catalytic activities of the new complexes have been compared with their N-methyl analogues for transfer hydrogenation of cyclohexanone and acceptorless dehydrogenation of benzyl alcohol. Furthermore, all complexes have been utilized as catalysts in the dehydrogenative coupling reaction of benzyl alcohol with amines. While the catalytic activities of the new complexes for transfer hydrogenation and acceptorless alcohol dehydrogenation were found to be in line with the previously observed trend based on the ancillary ligands (CO > COD > DMSO > PPh3), for the acceptorless dehydrogenative coupling reaction, complexes containing PPh3 and DMSO ligands performed better compared to complexes containing CO and COD ligands. Based on NMR and mass investigation of catalytic reactions, a plausible mechanism has been suggested to explain the difference in catalytic activity and its reversal during the dehydrogenative coupling reaction. Furthermore, the substrate scope for the dehydrogenative coupling reaction of benzyl alcohol with a wide range of amines has been explored, including synthesizing some pharmaceutically important imines. All new complexes have been characterized by various spectroscopic techniques, and the structures of 4b and 6b have been confirmed by the single-crystal X-ray diffraction technique.

Mechanistic investigation of electrocatalytic reductive amination at copper electrode.

Reductive amination has been widely used for manufacturing carbon-nitrogen-containing building blocks. Despite its versatility, the need for a chemical reductant or harmful hydrogen gas has limited its further utilization in modern chemical applications. Here, we report electrochemical reductive amination (ERA) to pursue sustainable synthetic routes. Faradaic efficiencies of about 83% are achieved using Cu metal electrodes. In-depth electrokinetic studies reveal the rate-determining step and overall reaction nature of ERA. Through the experiments using deuterated solvent and additional proton sources, we scrutinize the origin of protons during the ERA. Furthermore, CW-EPR analysis captures the radical intermediate species, formed during the catalytic cycle, advancing mechanistic understanding of ERA process.