Abstract
AbstractThe widespread use of pyridine‐based PNP pincer ligands has inspired the concept of metal‐ligand cooperation (MLC), in which the reactivity at the deprotonated CH2 (or NH) arm of the ligand is proposed to play an important role. Several groups developed a family of PNP‐type pincer ligands with methylated arms which were initially introduced to test the effect of blocking MLC in catalysis, but eventually led to unexpected consequences such as stabilization of unusual oxidation states, beneficial catalytic activity, or selectivity. Analysis of the sterics imposed by introducing Me groups revealed that arm protection can be an efficient tool to control sterics around the metal as an alternative to phosphine substitution, leading to much greater steric hinderance above and below pincer's coordination plane. This Concept will describe several illustrative examples which contrast the reactivity of classical CH2/NH‐arm PNP pincers with their CMe2/NMe‐armed counterparts, in particular related to Ru‐catalyzed alcohol dehydrogenative coupling, Fe‐catalyzed hydrogenation, hydroboration, and alkyne semihydrogenation.
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