System with Potential Dual Modes of Metal–Ligand Cooperation: Highly Catalytically Active Pyridine‐Based PNNH–Ru Pincer Complexes. Issue 48 (21st October 2014)

• Record Type: Journal Article
• Authors: Fogler, Eran; Garg, Jai Anand; Hu, Peng; Leitus, Gregory; Shimon, Linda J. W.; Milstein, David
• Is Part Of: Chemistry. Volume 20:Issue 48(2014)
• Page Start: 15727
• Page End: 15731
• Publication Date: 2014-10-21
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201405295
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Metal–ligand cooperation (MLC) plays an important role in catalysis. Systems reported so far are generally based on a single mode of MLC. We report here a system with potential for MLC by both amine–amide and aromatization–dearomatization ligand transformations, based on a new class of phosphino–pyridyl ruthenium pincer complexes, bearing <italic>sec</italic>‐amine coordination. These pincer complexes are effective catalysts under unprecedented mild conditions for acceptorless dehydrogenative coupling of alcohols to esters at 35 °C and hydrogenation of esters at room temperature and 5 atm H₂. The likely actual catalyst, a novel, crystallographically characterized monoanionic de‐aromatized enamido–Ru^II complex, was obtained by deprotonation of both the NH and the methylene proton of the N‐arm of the pincer ligand.</p> </abstract>