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dc.contributor.authorJian, Zhongbao
dc.contributor.authorFalivene, Laura
dc.contributor.authorWucher, Philipp
dc.contributor.authorRoesle, Philipp
dc.contributor.authorCaporaso, Lucia
dc.contributor.authorCavallo, Luigi
dc.contributor.authorGçttker-Schnetmann, Inigo
dc.contributor.authorMecking, Stefan
dc.date.accessioned2015-08-03T12:19:24Z
dc.date.available2015-08-03T12:19:24Z
dc.date.issued2014-12-08
dc.identifier.issn09476539
dc.identifier.doi10.1002/chem.201404856
dc.identifier.urihttp://hdl.handle.net/10754/563915
dc.description.abstractTwo series of cationic palladium(II) methyl complexes {[(2-MeOC6H4)2PC6H4SO2NHC6H3(2,6-R1,R2)]PdMe}2[A]2 (X1+-A: R1=R2=H: H1+-A; R1=R2=CH(CH3)2: DIPP1+-A; R1=H, R2=CF3: CF31+-A; A=BF4 or SbF6) and neutral palladium(II) methyl complexes {[(2-MeOC6H4)2PC6H4SO2NC6H3(2,6-R1,R2)]PdMe(L)} (X1-acetone: L=acetone; X1-dmso: L=dimethyl sulfoxide; X1-pyr: L=pyridine) chelated by a phosphine-sulfonamide were synthesized and fully characterized. Stoichiometric insertion of methyl acrylate (MA) into all complexes revealed that a 2,1 regiochemistry dominates in the first insertion of MA. Subsequently, for the cationic complexes X1+-A, β-H elimination from the 2,1-insertion product X2+-AMA-2,1 is overwhelmingly favored over a second MA insertion to yield two major products X4+-AMA-1,2 and X5+-AMA. By contrast, for the weakly coordinated neutral complexes X1-acetone and X1-dmso, a second MA insertion of the 2,1-insertion product X2MA-2,1 is faster than β-H elimination and gives X3MA as major products. For the strongly coordinated neutral complexes X1-pyr, no second MA insertion and no β-H elimination (except for DIPP2-pyrMA-2,1) were observed for the 2,1-insertion product X2-pyrMA-2,1. The cationic complexes X1+-A exhibited high catalytic activities for ethylene dimerization, affording butenes (C4) with a high selectivity of up to 97.7% (1-butene: 99.3%). Differences in activities and selectivities suggest that the phosphine-sulfonamide ligands remain coordinated to the metal center in a bidentate fashion in the catalytically active species. By comparison, the neutral complexes X1-acetone, X1-dmso, and X1-pyr showed very low activity towards ethylene to give traces of oligomers. DFT analyses taking into account the two possible coordination modes (O or N) of the sulfonamide ligand for the cationic system CF31+ suggested that the experimentally observed high activity in ethylene dimerization is the result of a facile first ethylene insertion into the O-coordinated PdMe isomer and a subsequent favored β-H elimination from the N-coordinated isomer formed by isomerization of the insertion product. Steric hindrance by the N-aryl substituent in the neutral systems CF31 and H1 appears to contribute significantly to a higher barrier of insertion, which accounts for the experimentally observed low activity towards ethylene oligomerization. Coordination switch: Analysis and comparison of the reactivity of new neutral and cationic PdII phosphine-sulfonamide complexes towards olefins in stoichiometric insertion and pressure-reactor experiments, complemented by DFT studies, elucidated the decisive factors for their catalytic behavior, including N versus O coordination modes (see figure).
dc.description.sponsorshipZ.J. is grateful to the Alexander von Humboldt Foundation for a postdoctoral research fellowship and to the University of Konstanz for a EU FP7 Marie Curie Zukunftskolleg Incoming Fellowship Programme (grant no. 291784).
dc.publisherWiley-Blackwell
dc.subjectCoordination modes
dc.subjectDensity functional calculations
dc.subjectDimerization
dc.subjectInsertion
dc.subjectPalladium
dc.titleInsights into functional-group-tolerant polymerization catalysis with phosphine-sulfonamide palladium (II) complexes
dc.typeArticle
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.contributor.departmentChemical Science Program
dc.identifier.journalChemistry - A European Journal
dc.contributor.institutionDepartment of Chemistry, University of KonstanzKonstanz, Germany
dc.contributor.institutionDepartment of Chemistry and Biology, University of Salerno, Via Giovanni Paolo IIFisciano (SA), Italy
kaust.personFalivene, Laura
kaust.personCavallo, Luigi
dc.relation.isSupplementedByJian, Z., Falivene, L., Wucher, P., Roesle, P., Caporaso, L., Cavallo, L., … Mecking, S. (2014). CCDC 973617: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11p40w
dc.relation.isSupplementedByDOI:10.5517/cc11p40w
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624288
dc.relation.isSupplementedByJian, Z., Falivene, L., Wucher, P., Roesle, P., Caporaso, L., Cavallo, L., … Mecking, S. (2014). CCDC 973618: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11p41x
dc.relation.isSupplementedByDOI:10.5517/cc11p41x
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624289
dc.relation.isSupplementedByJian, Z., Falivene, L., Wucher, P., Roesle, P., Caporaso, L., Cavallo, L., … Mecking, S. (2014). CCDC 973619: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11p42y
dc.relation.isSupplementedByDOI:10.5517/cc11p42y
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624290
dc.relation.isSupplementedByJian, Z., Falivene, L., Wucher, P., Roesle, P., Caporaso, L., Cavallo, L., … Mecking, S. (2014). CCDC 973620: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11p43z
dc.relation.isSupplementedByDOI:10.5517/cc11p43z
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624291
dc.relation.isSupplementedByJian, Z., Falivene, L., Wucher, P., Roesle, P., Caporaso, L., Cavallo, L., … Mecking, S. (2014). CCDC 973621: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11p440
dc.relation.isSupplementedByDOI:10.5517/cc11p440
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624292
dc.relation.isSupplementedByJian, Z., Falivene, L., Wucher, P., Roesle, P., Caporaso, L., Cavallo, L., … Mecking, S. (2014). CCDC 973622: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11p451
dc.relation.isSupplementedByDOI:10.5517/cc11p451
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624293
dc.relation.isSupplementedByJian, Z., Falivene, L., Wucher, P., Roesle, P., Caporaso, L., Cavallo, L., … Mecking, S. (2014). CCDC 977700: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11tcqy
dc.relation.isSupplementedByDOI:10.5517/cc11tcqy
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624299
dc.relation.isSupplementedByJian, Z., Falivene, L., Wucher, P., Roesle, P., Caporaso, L., Cavallo, L., … Mecking, S. (2014). CCDC 977701: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11tcrz
dc.relation.isSupplementedByDOI:10.5517/cc11tcrz
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624300


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