Exploring electronic and steric effects on the insertion and polymerization reactivity of phosphinesulfonato pdii catalysts

Handle URI:
http://hdl.handle.net/10754/563095
Title:
Exploring electronic and steric effects on the insertion and polymerization reactivity of phosphinesulfonato pdii catalysts
Authors:
Neuwald, Boris; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Mecking, Stefan
Abstract:
Thirteen different symmetric and asymmetric phosphinesulfonato palladium complexes ([{(X1-Cl)-μ-M}n], M=Na, Li, 1= X(P^O)PdMe) were prepared (see Figure 1). The solid-state structures of the corresponding pyridine or lutidine complexes were determined for (MeO)21-py, (iPrO)21-lut, (MeO,Me2)1-lut, (MeO)31-lut, CF31-lut, and Ph1-lut. The reactivities of the catalysts X1, obtained after chloride abstraction with AgBF4, toward methyl acrylate (MA) were quantified through determination of the rate constants for the first and the consecutive MA insertion and the analysis of β-H and other decomposition products through NMR spectroscopy. Differences in the homo- and copolymerization of ethylene and MA regarding catalyst activity and stability over time, polymer molecular weight, and polar co-monomer incorporation were investigated. DFT calculations were performed on the main insertion steps for both monomers to rationalize the effect of the ligand substitution patterns on the polymerization behaviors of the complexes. Full analysis of the data revealed that: 1) electron-deficient catalysts polymerize with higher activity, but fast deactivation is also observed; 2) the double ortho-substituted catalysts (MeO)21 and (MeO)31 allow very high degrees of MA incorporation at low MA concentrations in the copolymerization; and 3) steric shielding leads to a pronounced increase in polymer molecular weight in the copolymerization. The catalyst properties induced by a given P-aryl (alkyl) moiety were combined effectively in catalysts with two different non-chelating aryl moieties, such as cHexO/(MeO)21, which led to copolymers with significantly increased molecular weights compared to the prototypical MeO1. Catalyst control: The influence of steric and electronic effects on the reactivity of phosphinesulfonato PdII catalysts in polymerization and copolymerization is explored through experimental and DFT methods. A comparison of thirteen different X(P O)PdMe catalysts ((P O)= κ2-P,O-R1R2PC6H 4SO2O; see figure) reveals insights into the catalyst reactivity toward methyl acrylate and ethylene, their influence on the polymer microstructure, and the decomposition pathways. The unraveling of these relations provides guidelines for a directed choice of catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
21-Nov-2013
DOI:
10.1002/chem.201301365
Type:
Article
ISSN:
09476539
Sponsors:
This work was supported financially by the DFG (Me 1388/10). B.N. acknowledges support by the state of Baden-Wurttemberg by a Landesgraduiertenforderung-Stipend. The authors thank Anna-Lena Steck for high-resolution ESI-MS measurements, Alexander Klaiber for participation in this research as a part of his undergraduate studies, and the HPC team of Enea for use of the ENEA-GRID and the HPC facilities CRESCO in Portici, Italy.
Is Supplemented By:
Neuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933141: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b0bp; DOI:10.5517/cc10b0bp; HANDLE:http://hdl.handle.net/10754/624210; Neuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933140: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b09n; DOI:10.5517/cc10b09n; HANDLE:http://hdl.handle.net/10754/624209; Neuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933139: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b08m; DOI:10.5517/cc10b08m; HANDLE:http://hdl.handle.net/10754/624208; Neuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933138: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b07l; DOI:10.5517/cc10b07l; HANDLE:http://hdl.handle.net/10754/624207; Neuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933137: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b06k; DOI:10.5517/cc10b06k; HANDLE:http://hdl.handle.net/10754/624206; Neuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933136: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b05j; DOI:10.5517/cc10b05j; HANDLE:http://hdl.handle.net/10754/624205
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorNeuwald, Borisen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorMecking, Stefanen
dc.date.accessioned2015-08-03T11:35:39Zen
dc.date.available2015-08-03T11:35:39Zen
dc.date.issued2013-11-21en
dc.identifier.issn09476539en
dc.identifier.doi10.1002/chem.201301365en
dc.identifier.urihttp://hdl.handle.net/10754/563095en
dc.description.abstractThirteen different symmetric and asymmetric phosphinesulfonato palladium complexes ([{(X1-Cl)-μ-M}n], M=Na, Li, 1= X(P^O)PdMe) were prepared (see Figure 1). The solid-state structures of the corresponding pyridine or lutidine complexes were determined for (MeO)21-py, (iPrO)21-lut, (MeO,Me2)1-lut, (MeO)31-lut, CF31-lut, and Ph1-lut. The reactivities of the catalysts X1, obtained after chloride abstraction with AgBF4, toward methyl acrylate (MA) were quantified through determination of the rate constants for the first and the consecutive MA insertion and the analysis of β-H and other decomposition products through NMR spectroscopy. Differences in the homo- and copolymerization of ethylene and MA regarding catalyst activity and stability over time, polymer molecular weight, and polar co-monomer incorporation were investigated. DFT calculations were performed on the main insertion steps for both monomers to rationalize the effect of the ligand substitution patterns on the polymerization behaviors of the complexes. Full analysis of the data revealed that: 1) electron-deficient catalysts polymerize with higher activity, but fast deactivation is also observed; 2) the double ortho-substituted catalysts (MeO)21 and (MeO)31 allow very high degrees of MA incorporation at low MA concentrations in the copolymerization; and 3) steric shielding leads to a pronounced increase in polymer molecular weight in the copolymerization. The catalyst properties induced by a given P-aryl (alkyl) moiety were combined effectively in catalysts with two different non-chelating aryl moieties, such as cHexO/(MeO)21, which led to copolymers with significantly increased molecular weights compared to the prototypical MeO1. Catalyst control: The influence of steric and electronic effects on the reactivity of phosphinesulfonato PdII catalysts in polymerization and copolymerization is explored through experimental and DFT methods. A comparison of thirteen different X(P O)PdMe catalysts ((P O)= κ2-P,O-R1R2PC6H 4SO2O; see figure) reveals insights into the catalyst reactivity toward methyl acrylate and ethylene, their influence on the polymer microstructure, and the decomposition pathways. The unraveling of these relations provides guidelines for a directed choice of catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en
dc.description.sponsorshipThis work was supported financially by the DFG (Me 1388/10). B.N. acknowledges support by the state of Baden-Wurttemberg by a Landesgraduiertenforderung-Stipend. The authors thank Anna-Lena Steck for high-resolution ESI-MS measurements, Alexander Klaiber for participation in this research as a part of his undergraduate studies, and the HPC team of Enea for use of the ENEA-GRID and the HPC facilities CRESCO in Portici, Italy.en
dc.publisherWiley-Blackwellen
dc.subjectcatalysisen
dc.subjectcoordination modesen
dc.subjectdensity-functional calculationsen
dc.subjectkineticsen
dc.subjectreaction mechanismsen
dc.subjecttheoretical chemistryen
dc.titleExploring electronic and steric effects on the insertion and polymerization reactivity of phosphinesulfonato pdii catalystsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalChemistry - A European Journalen
dc.contributor.institutionDepartment of Chemistry, University of Konstanz, 78464 Konstanz, Germanyen
dc.contributor.institutionDepartment of Chemistry and Biology, University of Salerno, Via Giovanni Paolo II, 132, 84084 - Fisciano (SA), Italyen
kaust.authorCavallo, Luigien
dc.relation.isSupplementedByNeuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933141: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b0bpen
dc.relation.isSupplementedByDOI:10.5517/cc10b0bpen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624210en
dc.relation.isSupplementedByNeuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933140: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b09nen
dc.relation.isSupplementedByDOI:10.5517/cc10b09nen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624209en
dc.relation.isSupplementedByNeuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933139: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b08men
dc.relation.isSupplementedByDOI:10.5517/cc10b08men
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624208en
dc.relation.isSupplementedByNeuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933138: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b07len
dc.relation.isSupplementedByDOI:10.5517/cc10b07len
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624207en
dc.relation.isSupplementedByNeuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933137: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b06ken
dc.relation.isSupplementedByDOI:10.5517/cc10b06ken
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624206en
dc.relation.isSupplementedByNeuwald, B., Falivene, L., Caporaso, L., Cavallo, L., & Mecking, S. (2014). CCDC 933136: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10b05jen
dc.relation.isSupplementedByDOI:10.5517/cc10b05jen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624205en
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