Plastically deformed Cu-based alloys as high-performance catalysts for the reduction of 4-nitrophenol

Catal. Sci. Technol., 2016, Advance Article
DOI: 10.1039/C6CY00734A, Paper
Eredzhep Menumerov, Kyle D. Gilroy, Maryam Hajfathalian, Colin J. Murphy, Erica R. McKenzie, Robert A. Hughes, Svetlana Neretina
Plastically deformed mesoscopic structures exposed to an etching procedure are demonstrated as highly catalytic in the reduction of 4-nitrophenol.

Plastically deformed Cu-based alloys as high-performance catalysts for the reduction of 4-nitrophenol

Plastically deformed Cu-based alloys as high-performance catalysts for the reduction of 4-nitrophenol

The severe plastic deformation of metals leads to the formation of nanotextured surfaces as well as the retention of significant strain energy, characteristics which are known to promote catalytic activity. Here, we demonstrate plastically deformed surfaces of copper and copper-based alloys as being highly catalytic using the well-studied model catalytic reaction which reduces 4-nitrophenol to 4-aminophenol by borohydride. Among the materials studied, the most catalytically active is formed in a two-step process where metal chips are mechanically sheared from a Cu–Sn alloy containing precipitates and then exposed to an etchant which removes the precipitates from the exposed surface. The so-formed structures exhibit exceedingly high catalytic activity and set new benchmarks when incorporated into a fixed-bed reactor. The formation of catalytically active sites is shown to be strongly dependent on the presence of the precipitates during the deformation process, achieving an order of magnitude increase in the reaction rate constant when compared to similarly formed Cu–Sn catalysts lacking these precipitates. The work, therefore, demonstrates a new approach for generating catalytically active sites which may be applicable to other alloy combinations.


////Plastically deformed, Cu-based alloys,  high-performance catalysts,  reduction, 4-nitrophenol


Ni-Catalyzed Reduction of Inert C-O Bonds: A New Strategy for Using Aryl Ethers as Easily Removable Directing Groups

Ni-Catalyzed Reduction of Inert C-O Bonds: A New Strategy for Using Aryl Ethers as Easily Removable Directing Groups

Most synthetic chemists are used to employ aryl methyl ethers as directing groups. They are powerful directors in substitution reactions, metallations and others. But once you are done, you are stick with them. They are not easy to remove, though some methods existed. Now, Martin et al. (ICIQ, Spain) have developed a catalytic method for the reduction of those ‘inert’ C-O bonds.
The method relies in the use of Ni(COD)2 (5-10 mol%), PCy3 (10-20 mol%), TMDSO as reducing agent (1 equiv) in toluene at 110 °C for 8-14 h. The results are quite good and a number of substrates are demethoxylated. The protocol leaves benzylic methyl ethers, methyl esters and others untouched. As demonstration of its applicability, the authors have prepared some substrates by ortho-metallation, removing then the OMe group to reach ‘magically’ prepared substrates, even with the troublesome 1,3-substitution pattern. I have already in mind a couple of substrates which we would like to test…
J. Am. Chem. Soc., 2010, 132 (49), pp 17352–17353. See: 10.1021/ja106943q


Combined experimental and theoretical study on the reductive cleavage of inert C?O bonds with silanes: Ruling out a classical Ni(0)/Ni(II) catalytic couple and evidence for Ni(I) intermediates

J. Cornella, E. Gómez-Bengoa, R. Martin
J. Am. Chem. Soc. 2013, 135, 1997-2009

A mechanistic and computational study on the reductive cleavage of C-OMe bonds catalyzed by Ni(COD)2/PCy3 with silanes as reducing agents is reported herein. Specifically, we demonstrate that the mechanism for this transformation does not proceed via oxidative addition of the Ni(0) precatalyst into the C-OMe bond. In the absence of an external reducing agent, the in-situ-generated oxidative addition complexes rapidly undergo β-hydride elimination at room temperature, ultimately leading to either Ni(0)-carbonyl- or Ni(0)-aldehyde-bound complexes. Characterization of these complexes by X-ray crystallography unambiguously suggested a different mechanistic scenario when silanes are present in the reaction media. Isotopic-labeling experiments, kinetic isotope effects, and computational studies clearly reinforced this perception. Additionally, we also found that water has a deleterious effect by deactivating the Ni catalyst via formation of a new Ni-bridged hydroxo species that was characterized by X-ray crystallography. The order in each component was determined by plotting the initial rates of the C-OMe bond cleavage at varying concentrations. These data together with the in-situ-monitoring experiments by 1H NMR, EPR, IR spectroscopy, and theoretical calculations provided a mechanistic picture that involves Ni(I) as the key reaction intermediates, which are generated via comproportionation of initially formed Ni(II) species. This study strongly supports that a classical Ni(0)/Ni(II) for C-OMe bond cleavage is not operating, thus opening up new perspectives to be implemented in other related C-O bond-cleavage reactions.

Read all about Organic Spectroscopy on ORGANIC SPECTROSCOPY INTERNATIONAL 


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