Topics in Catalysis

, Volume 53, Issue 13, pp 915–923

Discovery of Environmentally Benign Catalytic Reactions of Alcohols Catalyzed by Pyridine-Based Pincer Ru Complexes, Based on Metal–Ligand Cooperation


DOI: 10.1007/s11244-010-9523-7

Cite this article as:
Milstein, D. Top Catal (2010) 53: 915. doi:10.1007/s11244-010-9523-7


We have developed a new mode of metal–ligand cooperation, based on aromatization–dearomatization of pyridine-based pincer-type ligands, and have demonstrated it in the activation of H2 and C–H bonds by PNP Ir complexes. This type of metal–ligand cooperation plays a key role in the recently discovered environmentally benign reactions of alcohols, catalyzed by PNP and PNN pincer complexes of ruthenium, including (a) dehydrogenation of secondary alcohols to ketones (b) dehydrogenative coupling of primary alcohols to form esters and H2 (c) hydrogenation of esters to alcohols under mild conditions (d) unprecedented amide synthesis: catalytic coupling of amines with alcohols, with liberation of H2. Ligand modification in the latter reaction has led to unprecedented synthesis of imines with H2 liberation. These reactions are very efficient, proceed under neutral conditions and produce no waste.


Pincer complexes Metal–ligand cooperation Acohols Amines Amides Imines Dehydrogenative coupling Hydrogen Ruthenium Iridium Catalysis O–H activation C–H activation PNP PNN 

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© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  1. 1.Department of Organic ChemistryThe Weizmann Institute of ScienceRehovotIsrael