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Molecules 2014, 19(9), 15116-15161;

Carbonylation of Ethene Catalysed by Pd(II)-Phosphine Complexes

Department of Chemical Sciences, University of Padua, Padua 35131, Italy
Department of Molecular Sciences and Nanosystems, Ca' Foscari University of Venice, Venice 30123, Italy
Author to whom correspondence should be addressed.
Received: 2 July 2014 / Revised: 2 September 2014 / Accepted: 11 September 2014 / Published: 22 September 2014
(This article belongs to the Special Issue Carbonylation Chemistry)
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This review deals with olefin carbonylation catalysed by Pd(II)-phosphine complexes in protic solvents. In particular, the results obtained in the carbonylation with ethene are reviewed. After a short description of the basic concepts relevant to this catalysis, the review treats in greater details the influence of the bite angle, skeletal rigidity, electronic and steric bulk properties of the ligand on the formation of the products, which range from high molecular weight perfectly alternating polyketones to methyl propanoate. It is shown that the steric bulk plays a major role in directing the selectivity. Particular emphasis is given to the factors governing the very active and selective catalysis to methyl propanoate, including the mechanism of the catalytic cycles with diphosphine- and monophosphine-catalysts. A brief note on the synthesis of methyl propanoate using a “Lucite” type catalyst in ionic liquids is also illustrated. A chapter is dedicated to the carbonylation of olefins in aqueous reaction media. The nonalternating CO-ethene copolymerization is also treated. View Full-Text
Keywords: carbonylation; ethene; palladium-phosphine; catalysts carbonylation; ethene; palladium-phosphine; catalysts

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Cavinato, G.; Toniolo, L. Carbonylation of Ethene Catalysed by Pd(II)-Phosphine Complexes. Molecules 2014, 19, 15116-15161.

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