Unveiling the role of ancillary ligands in acceptorless benzyl alcohol dehydrogenation and etherification mediated by
Ángela Vivancos1, Ana Petronilho, Joao Cardoso
1Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
Abstract:
We synthesized a set of triazolylidene iridium(iii) complexes [IrCp*(C^N)L]n+ (Cp* = pentamethylcyclopentadienyl, C^N = C,N-bidentate coordinating pyridyl-triazolylidene) containing different neutral or anionic ancillary ligands L and evaluated their impact on the catalytic activity in alcohol conversion. We demonstrate that these ancillary ligands have a strong influence on the catalytic selectivity and direct whether the iridium center preferentially catalyzes either the dehydrogenation or the dehydration of benzyl alcohol. Ligand exchange experiments provide a direct correlation of ligand lability with catalytic activity and selectivity. These results underline the relevance of ancillary ligands and provide a rational approach to tailor the catalytic activity of the iridium center towards aldehyde formation (loss of H2) or etherification (elimination of H2O).
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