Ruthenium(II) PNN complexes depolymerize many polyesters into diols and polycarbonates into glycols plus methanol via hydrogenation. Notably, polyesters with two methylene units between ester linkages depolymerize to carboxylic acids rather than diols. This methodology represents a new approach for producing useful chemicals from waste plastics.
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Autocatalytic Activation of a Ruthenium-PNN-Pincer Hydrogenation Catalyst.
ACS Catal
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Department of Chemistry, Colgate University, 13 Oak Drive, Hamilton, New York 13346, United States.
In this article, we describe a detailed experimental and computational study of the activation mechanism for a highly active pincer ruthenium(0) precatalyst for the hydrogenation of polar organic compounds. The precatalyst activates by reaction with 2 equiv of hydrogen, resulting in a net oxidative addition to ruthenium and hydrogenation of an imine functional group on the supporting ligand. The kinetics of precatalyst hydrogenation were measured by UV-visible spectroscopy under catalytically relevant conditions (10-39 bar hydrogen, 298 K).
View Article and Find Full Text PDFRuthenium complexes featuring cooperative phosphine-pyridine-iminophosphorane (PNN) ligands: synthesis, reactivity and catalytic activity.
Dalton Trans
October 2018
LCM, CNRS-Ecole polytechnique, Université Paris-Saclay, F-91128 Palaiseau Cedex, France.
The coordination to ruthenium(ii) centres of two phosphine-pyridine-iminophosphorane ligands LR (PPh2CH2(C6H3N)CH2N[double bond, length as m-dash]PR3, R = Ph or Cy) differing by the nature of the substituent of the P[double bond, length as m-dash]N phosphorus was explored. Coordination to [RuCl2(PPh3)3] afforded the complexes [RuLRCl2(PPh3)] that were successfully deprotonated at the acidic phosphinomethyl position. With LCy, coordination led to a mixture of two isomers.
View Article and Find Full Text PDFControlled hydrogenative depolymerization of polyesters and polycarbonates catalyzed by ruthenium(II) PNN pincer complexes.
Chem Commun (Camb)
May 2014
Northland College, 1411 Ellis Ave., Ashland, Wisconsin 54806, USA.
Ruthenium(II) PNN complexes depolymerize many polyesters into diols and polycarbonates into glycols plus methanol via hydrogenation. Notably, polyesters with two methylene units between ester linkages depolymerize to carboxylic acids rather than diols. This methodology represents a new approach for producing useful chemicals from waste plastics.
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