Work

Methylene-Linked Triazolylidenes as Cooperative Ligands in Manganese-Catalyzed N -Alkylation

Year: 2026

Type: article

Abstract: -alkylation of aniline with benzyl alcohol mediated by a bis(1,2,3-triazolylidene) Mn(I) complex through a combination of experimental studies and density functional theory (DFT) calculations. Activation of the precatalyst by a base leads to the formation of an anionic alkoxo complex featuring a deprotonated methylene bridge, which is identified as the catalytically active species. Notably, the methylene linker exhibits previously unrecognized noninnocent behavior, undergoing reversible deprotonation and participating directly in proton-transfer steps of the catalytic cycle. Kinetic isotope effects and deuterium-labeling experiments support the involvement of both hydride transfer and alcohol-assisted proton processes in the rate-determining steps. These findings uncover a new mode of metal-ligand cooperation in triazolylidene-based manganese catalysts and provide mechanistic guidelines for the design of cooperative ligands in base-metal-borrowing hydrogen catalysis.

Source: Inorganic Chemistry

DOI: 10.1021/acs.inorgchem.6c01357

Authors: Maria Batuecas, Beatriz Garcia, Chiara Saviozzi, Maria S. Viana, Feliu Maseras, Beatriz Royo