Catalytic Mechanisms of Transfer Hydrogenation of Azobenzene with Ammonia Borane by Pincer Bismuth Complex: Crucial Role of C=N Functional Group on the Pincer Ligand

Transfer hydrogenation of azobenzene with ammonia borane mediated by pincer bismuth complex 1 was systematically investigated through density functional theory calculations. An unusual metal-ligand cooperation mechanism was disclosed, in which the saturation/regeneration of the C=N functional group on the pincer ligand plays an essential role. The reaction is initiated by the hydrogenation of the C=N bond (saturation) with ammonia borane to afford 3(CN), which is the rate-determining step with Gibbs energy barrier (Delta G(not equal)) and Gibbs reaction energy (Delta G) of 25.6 and -7.3kcal/mol, respectively. 3(CN) is then converted to a Bi-H intermediate through a water-bridged pathway, which is followed up with the transfer hydrogenation of azobenzene to produce the final product N,N '-diphenylhydrazine and regenerate the catalyst. Finally, the catalyst could be improved by substituting the phenyl group for the tert-butyl group on the pincer ligand, where the Delta G(not equal) value (rate-determining step) decreases to 24.0kcal/mol.

Automated summary

The transfer hydrogenation of azobenzene with ammonia borane mediated by pincer bismuth complex 1 was studied using density functional theory calculations. The study revealed an unusual metal-ligand cooperation mechanism involving the saturation/regeneration of the C=N functional group on the pincer ligand. The reaction proceeds through the hydrogenation of the C=N bond, followed by the conversion of 3(CN) to a Bi-H intermediate, and eventually results in the production of N,N'-diphenylhydrazine and regeneration of the catalyst. The substitution of the phenyl group with a tert-butyl group on the pincer ligand improves the catalyst's performance.