The field of metal-ligand cooperative catalysis has expanded greatly in recent years due to the development of a diversity of ligand scaffolds. The pendent amine of the PR2NR’2 ligand family was designed to shuttle protons in electrocatalysis, but the ligand family has received little attention in MLC catalysis for organic transformations. We have prepared a series of [Ru(Cp)(PR2NR’2)(MeCN)]PF6 complexes that are active metal-ligand cooperative catalysts toward acceptorless dehydrogenation of amines. Catalyst performance studies reveal that the pendent amine is integral for both catalyst activity and selectivity. However, the amine also stabilizes a deactivation species that likely tempers catalyst activity. Strategies to maximize productive reactivity will be discussed, including catalyst redesign through modification of the R and R’ substituents of the ligand.

Asset or achilles heel? The role of the pendent base in metal-ligand cooperative dehydrogenation catalysis

255th National Meeting (2018)

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