Bidentate Triazolate-Based Ligand System: Synthesis, Coordination Modes, and Cooperative Bond Activation

Abstract

The 1,2,3-triazole ring represents a highly attractive and useful platform for ligand synthesis. In this work, we reveal the design, preparation, and properties of a novel bidentate triazolatebased ligand and its potential in cooperative metal−ligand bond activation. Our triazolate system exhibits a multiphase mode of coordination to transition metals, supporting both dimeric and monomeric complexes. The complexes were carefully characterized both in solution and in the solid state. The metal−ligand cooperative potential of the basic triazolate pattern was demonstrated in HCl and H−H bond activation.

Metal–Ligand Cooperative Catalytic Coupling of Terminal Alkynes and Carboxylic Acids for the Stereoselective Synthesis of Dienyl Esters

“…The triazole unit in these species serves as an internal base, and we believe that the process of cooperative activation is relatively facile due to the strain of the four-membered ring in the starting complex A1, which is released upon opening in the activation process. 6 We aimed to extend the M−L cooperative activation process to mildly acidic carboxylic acids and to study the catalytic cooperative addition of RCO 2 H to unsaturated carbon−carbon bonds (olefins and alkynes). Searching for a proper metal candidate, we focused our efforts on ruthenium, which proved highly efficient in the cooperative activation of O−H bonds in various catalytic processes.…”

“…Moreover, we demonstrated that complexes A1 could cooperatively activate both polar and nonpolar H–X bonds (X = H, Cl). The triazole unit in these species serves as an internal base, and we believe that the process of cooperative activation is relatively facile due to the strain of the four-membered ring in the starting complex A1 , which is released upon opening in the activation process . We aimed to extend the M–L cooperative activation process to mildly acidic carboxylic acids and to study the catalytic cooperative addition of RCO 2 H to unsaturated carbon–carbon bonds (olefins and alkynes).…”