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The influence of oscillations on product selectivity during the palladium-catalysed phenylacetylene oxidative carbonylation reaction

Lookup NU author(s): Dr Katarina Novakovic, Dr Christophe Grosjean, Dr Mark Willis, Professor Allen Wright



This paper reports on the influence of oscillations on product selectivity as well as the dynamics of product formation during the palladium-catalysed phenylacetylene oxidative carbonylation reaction in a catalytic system (PdI 2, KI, Air, NaOAc in methanol). The occurrence of the pH oscillations is related to PdI2 granularity and the initial pH drop after phenylacetylene addition. To achieve pH and reaction exotherm oscillations regulation of the amount of PdI2 is required, ensuring that the initial pH does not fall significantly below 1 after phenylacetylene addition. Experiments in both oscillatory and non-oscillatory pH regimes were performed in an HEL SIMULAR™ reaction calorimeter with the concentration-time profiles measured using a GC-MS. It is demonstrated that when operating in an oscillatory pH regime product formation may be suppressed until oscillations occur after which there is a steep increase in the formation of Z-2-phenyl-but-2-enedioic acid dimethyl ester. When operating in non-oscillatory pH mode the products are formed steadily over time with the main products being Z-2-phenyl-but-2-enedioic acid dimethyl ester, 2-phenyl-acrylic acid methyl ester and E-3-phenyl-acrylic acid methyl ester. © the Owner Societies.

Publication metadata

Author(s): Novakovic K, Grosjean C, Scott SK, Whiting A, Willis MJ, Wright AR

Publication type: Article

Publication status: Published

Journal: Physical Chemistry Chemical Physics

Year: 2008

Volume: 10

Issue: 5

Pages: 749-753

Print publication date: 01/01/2008

Date deposited: 05/07/2010

ISSN (print): 1463-9076

ISSN (electronic): 1463-9084

Publisher: Royal Society of Chemistry


DOI: 10.1039/b713906c


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