Abstract
• Acceptorless dehydrogenation of alcohols to high value chemicals by homogeneous catalysts. • Acceptorless dehydrogenation of alcohols for future applications as hydrogen storage systems. • Multifunctional ligands in the coordination sphere of a metal center to improve catalytic activity. • Novel metal–ligand cooperativity to enable non-precious metal catalysis. Catalytic dehydrogenation of alcohols represents an attractive approach for future applications as hydrogen storage systems and clean synthesis of fine chemicals. Herein, an overview of recent progress in homogeneously catalyzed acceptorless alcohol dehydrogenation is presented. In Nature, dehydrogenation of alcohols is efficiently catalyzed by multiple metalloenzymes where a non-noble metal–ligand interplay is key to activate and transform a substrate. We highlight the introduction of multifunctional cooperative ligands in the coordination sphere of the metal center in order to improve catalytic activity under photochemical, electrochemical or thermal conditions. Moreover, metal–ligand cooperativity is crucial for an easy transition to first row metal based catalysis, as we have seen in the recent years.
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