Control of Polymer Composition in Pd‐Catalyzed CO/Olefin Terpolymerization Reactions

Bastero, Amaia; Ruiz, Aurora; Claver, Carmen; Bella, A. Franco; Milani, Barbara; Moreno-Lara, Belén; Jalón, Félix A.; Manzano, Blanca R.

doi:10.1002/adsc.200404344

Cited by 15 publications

(4 citation statements)

References 28 publications

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“…[51] This effect is shown in Figure 10 The cationic palladium systems [PdMe(NCMe)(N-NЈ)]-[BArF] containing imidazolyl-pyridine ligands cis-12, cis-13, cis-and trans-15 and pyrazolyl-pyridines 18, 20 and 21 have also been used for the terpolymerisation of CO/TBS/ ethene. [50,52] It was found that the choice of the olefin preferentially inserted into the terpolymer is strictly related to the nature of the nitrogen ligand present in the catalyst and not only to the kind of ligand. Thus, a slight modification in the chelating N ligands coordinated to palladium terpolymerisation catalysts leads to unexpected results in the composition of the terpolymers.…”

Section: Modular N-nј Ligands For the Copolymerisation Of Co And Styrenementioning

confidence: 99%

Alternating and Non‐Alternating Pd‐Catalysed Co‐ and Terpolymerisation of Carbon Monoxide and Alkenes

et al. 2007

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The co-and terpolymerisation of carbon monoxide and alkenes are usually catalysed by palladium complexes, and the properties of the produced polyketones can be finely tuned by an appropriate choice of catalyst and olefinic monomer. After a general overview of the topic, selected recent advances in this field are described. The use of palladium systems containing modified diphosphane and/or new phospho-

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Section: Modular N-nј Ligands For the Copolymerisation Of Co And Styrenementioning

confidence: 99%

Alternating and Non‐Alternating Pd‐Catalysed Co‐ and Terpolymerisation of Carbon Monoxide and Alkenes

et al. 2007

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“…More recently, the use of the cationic palladium systems [PdMe(NCMe)(N -N ′ )] [BArF] containing pyridine -imidazoline ligands cis -107a , cis -107b , and cis and trans -107d was reported in the terpolymerization of CO/TBS/ethane, and circular dichroism analysis of the terpolymer obtained with the enantiomerically pure ligand 107d shows that it is optically active [119] .…”

Section: Asymmetric Co /Olefi Ns Terpolymerizationmentioning

confidence: 99%

Asymmetric Carbonylations

Godard

Ruiz

Diéguez

et al. 2010

Catalytic Asymmetric Synthesis

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Transition metal -catalyzed carbonylation is one of the most straightforward tools to obtain fi ne chemicals intermediates from alkenes and other unsaturated products. Together with asymmetric hydrogenation, asymmetric C -C bond formation, and asymmetric allylic substitutions, the asymmetric carbonylations are among the most challenging homogeneous processes. Their potential is still to be made the most of, perhaps because of the complexity of these reactions where aldehydes, esters, or acids can be formed from simple olefi ns and enantiomerically pure products or enantiomeric enrichment of one of the products can be obtained when the transition metal catalyst is modifi ed with a chiral ligand. The most famous asymmetric carbonylation process is the Rh -catalyzed hydroformylation of alkenes, together with the Pd -catalyzed hydroxy -or alkoxycarbonylation of alkenes. There are, however, important differences between these processes, as the rhodium -catalyzed hydroformylation is of greater industrial interest than the palladium carbonylations. From the mechanistic point of view, rhodiumcatalyzed hydroformylation has been much more studied and understood than the palladium -catalyzed carbonylations maybe because of the stability of rhodium species, as well as the applicability of spectroscopic high -pressure (HP) nuclear magnetic resonance (NMR) techniques for the study of the intermediates and the early application of rhodium hydroformylation in industry as " oxo " process. As a result, the last developments in rhodium -catalyzed hydroformylation led to a very good control of the regioselectivity to the desired product as well as the preparation of practically enantiomerically pure aldehydes. Palladium -catalyzed carbonylations, both alkoxycarbonylation and hydroxycarbonylation, have also been widely studied but present more issues to obtain Catalytic Asymmetric Synthesis, Third Edition, Edited by Iwao Ojima

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“…We have previously shown that in the CO/tert-butylstyrene/ethylene terpolymerization catalyzed by ½PdðMeÞðNCMeÞðN -N 0 Þ½BAr 0 4 complexes [Ar 0 = 3,5-(CF 3 ) 2 C 6 H 3 ], where N-N 0 = pyridine-imidazoline and pyrazolyl-pyrimidine ligands, the olefin preferentially inserted in the terpolymer chain is strictly related to the nature of the nitrogen ligand [27].…”

Section: Introductionmentioning

confidence: 99%

Pyrazolyl-pyrimidine based ligands in palladium catalyzed copolymerization and terpolymerization of CO/olefins

Bella

Ruiz

Claver

et al. 2008

Journal of Organometallic Chemistry

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Control of Polymer Composition in Pd‐Catalyzed CO/Olefin Terpolymerization Reactions

Cited by 15 publications

References 28 publications

Alternating and Non‐Alternating Pd‐Catalysed Co‐ and Terpolymerisation of Carbon Monoxide and Alkenes

Alternating and Non‐Alternating Pd‐Catalysed Co‐ and Terpolymerisation of Carbon Monoxide and Alkenes

Asymmetric Carbonylations

Pyrazolyl-pyrimidine based ligands in palladium catalyzed copolymerization and terpolymerization of CO/olefins

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