Carbonylation of ethene

Carbonylation of Ethene in Methanol Catalysed by Cationic Phosphine Complexes of Pd(ll) from Polyketones to Monocarbonylated Products... 

The carbonylation of ethene has a wider interest as it can lead to the production not only of polyketones, but also to many other products ranging from low molecular weight cooligoesters, down to methyl propanoate (MP) and also cooligodiesters, cooligodiketones down to diethyl ketone (DEK). The insertion of the monomers into MeOH is schematized by Eq. 1, n ranging from 1 to even more that 10000 ... 

Hereafter, the factors ruling the activity and selectivity of Pd(II)-phosphine catalysts for the carbonylation of ethene in MeOH are presented. In order to make the exposition clearer some of the concepts already discussed in other reviews will be shortly resumed. It will deal first with copolymerisation because it includes more general aspects, several of which are involved also in the catalysis to monocarbonylated non-polymeric products. The literature search covers all up to 2004. 

Catellani M (2005) Novel Methods of Aromatic Functionalization Using Palladium and Norbornene as a Unique Catalytic System. 14 21-54 Cavinato G, Toniolo L, Vavasori A (2006) Carbonylation of Ethene in Methanol Catalysed by Cationic Phosphine Complexes of Pd(II) from Polyketones to Monocarbonylated Products. 18 125-164... 

The carbon of complexed CO, i. e., M-CO, can appear at either a lower or higher frequency than CO itself depending on the metal. A useful list of CO chemical shifts can be found in a study describing mechanistic aspects of the Rh- and Ir-cat-alyzed carbonylation of methanol [59]. Additional C NMR data on Rh-acyl intermediates, derived from the Rh-catalyzed carbonylation of ethene, e. g., 60, have been reported [60]. 

The substitution of nickel for palladium catalyst precursors has, in principle, two advantages the lower price of the metal and the lower tendency to plate. The effectiveness of nickel in the carbonylation of ethene to low molecular weight polyketones has been known for a long time [4]. Only recently, however, have nickel catalyst precursors with a reasonably high catalytic activity been discovered. The newest compounds are nickel complexes, which are modified by semicorrine-type ligands (Scheme 8.10). 

N. M. (2007) Ester versus polyketone formation in the palladium-diphosphine catalyzed carbonylation of ethene. 

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