RuII complexes of 1,2,3-triazole appended tertiary phosphines, [P(Ph){(o-C6H4)(1,2,3-N3C(Ph)CH}2] and [P(Ph){o-C6H4(CCH)-(1,2,3-N3-Ph)}2]: highly active catalysts for transfer hydrogenation of carbonyl/nitro compounds and for α-alkylation of ketones

The synthesis of two new 1,2,3-triazole appended monophosphines [P(Ph){(o-C6H4)(1,2,3-N3C(Ph)CH}(2)] (1) and [P(Ph){o-C6H4(CCH)(1,2,3-N-3-Ph)}(2)] (2) and their Ru-II complexes is described. The reactions of 1 and 2 with [Ru(PPh3)(3)Cl-2] in a 1 : 1 molar ratio produced cationic complexes 3 and 4, respectively. Both the complexes showed very high catalytic activity towards transfer hydrogenation, nitro reduction, and alpha-alkylation reactions and afforded the corresponding products in good to excellent yields. The free energy of beta-hydride elimination from the respective Ru-alkoxide intermediates, a key mechanistic step common to all the three catalytic pathways, was calculated to be close to ergoneutral by density functional theory-based calculations, which is posited to rationalize the catalytic activity of 3. The reduction of aromatic nitro compounds was found to be highly chemoselective and produced the corresponding amines as major products even in the presence of a carbonyl group. The triazolyl-N2 coordinated Ru-II-NPN complex 3 showed better catalytic activity compared to the triazolyl-N3 coordinated complex 4.

Automated summary

The synthesis and catalytic activity of two new 1,2,3-triazole appended monophosphines and their Ru-II complexes were investigated, showing high efficiency in transfer hydrogenation, nitro reduction, and alpha-alkylation reactions.