Controlled acrylate insertion regioselectivity in diazaphospholidine- sulfonato palladium(II) complexes

Handle URI:
http://hdl.handle.net/10754/562465
Title:
Controlled acrylate insertion regioselectivity in diazaphospholidine- sulfonato palladium(II) complexes
Authors:
Wucher, Philipp; Roesle, Philipp; Falivene, Laura; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Caporaso, Lucia; Göttker-Schnetmann, Inigo J.; Mecking, Stefan
Abstract:
Diazaphospholidine-sulfonato Pd(II) complexes [{κ2-P,O-(N- Ar2C2H4N2P)C6H 4SO3}PdMe(L)] 1-L (L = dmso, pyridine, lutidine, or μ-LiCl(solvent); 1a: Ar = Ph, 1b: Ar = 2-MeC6H4, 1c: Ar = 2-MeOC6H4, 1d: Ar = 2,4,6-Me3C 6H2, 1e: Ar = 2,6-iPr2C6H 3, 1f: Ar = 2,6-(p-tolyl)2C6H3) were prepared and structurally characterized. The regioselectivity of methyl acrylate (MA) insertion into the Pd-Me bond is entirely inverted from >93% 1,2-insertion for bulky substituents (1d-f, yielding the insertion products [(P̂O)Pd{κ2-C,O-CH2CHMeC(O)OMe], 12) to the usual electronically controlled 2,1-insertion (>95%) for the less bulky Ar = Ph (1a, yielding the insertion product [(P̂O)Pd{κ2-C,O- CHEtC(O)OMe], 11, and β-H elimination product methyl crotonate). DFT studies underline that this is due to a more favorable insertion transition state (2,1- favored by 12 kJ mol-1 over 1,2- for 1a) vs destabilization of the 2,1-insertion transition state in 1d,e. By contrast, MA insertion into the novel isolated and structurally characterized hydride and deuteride complexes [{κ2-P,O-(N-Ar2C 2H4N2P)C6H4SO 3}PdR(lutidine)] (Ar = 2,6-iPr2C6H3; 9e: R = H, 10e: R = D) occurs 2,1-selectively. This is due to the insertion occurring from the isomer with the P-donor and the olefin in trans arrangement, rather than the insertion into the alkyl from the cis isomer in which the olefin is in proximity to the bulky diazaphospholidine. 1a-f are precursors to active catalysts for ethylene polymerization to highly linear polyethylene with M n up to 35 000 g mol-1. In copolymerization experiments, norbornene was incorporated in up to 6.1 mol % into the polyethylene backbone. © 2012 American Chemical Society.
KAUST Department:
Biological and Environmental Sciences and Engineering (BESE) Division; KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
24-Dec-2012
DOI:
10.1021/om300755j
Type:
Article
ISSN:
02767333
Sponsors:
Financial support by the DFG (Me1388/10-1) is gratefully acknowledged. The authors thank Lars Bolk for GPC, Anke Friemel and Ulrich Haunz for support with NMR measurements, and the HPC team of Enea (www.enea.it) for use of the ENEA-GRID and the HPC facilities CRESCO (www.cresco.enea.it) in Portici, Italy.
Is Supplemented By:
Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894982: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19dp; DOI:10.5517/ccz19dp; HANDLE:http://hdl.handle.net/10754/624732; Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894983: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19fq; DOI:10.5517/ccz19fq; HANDLE:http://hdl.handle.net/10754/624733; Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894984: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19gr; DOI:10.5517/ccz19gr; HANDLE:http://hdl.handle.net/10754/624734; Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894985: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19hs; DOI:10.5517/ccz19hs; HANDLE:http://hdl.handle.net/10754/624735; Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894986: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19jt; DOI:10.5517/ccz19jt; HANDLE:http://hdl.handle.net/10754/624736; Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894987: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19kv; DOI:10.5517/ccz19kv; HANDLE:http://hdl.handle.net/10754/624737; Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894988: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19lw; DOI:10.5517/ccz19lw; HANDLE:http://hdl.handle.net/10754/624738; Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894989: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19mx; DOI:10.5517/ccz19mx; HANDLE:http://hdl.handle.net/10754/624739; Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894990: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19ny; DOI:10.5517/ccz19ny; HANDLE:http://hdl.handle.net/10754/624740; Wucher, P., Roesle, P., Falivene, L., Cavallo, L., Caporaso, L., Göttker-Schnetmann, I., & Mecking, S. (2013). CCDC 894991: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccz19pz; DOI:10.5517/ccz19pz; HANDLE:http://hdl.handle.net/10754/624741
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorWucher, Philippen
dc.contributor.authorRoesle, Philippen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorGöttker-Schnetmann, Inigo J.en
dc.contributor.authorMecking, Stefanen
dc.date.accessioned2015-08-03T10:39:11Zen
dc.date.available2015-08-03T10:39:11Zen
dc.date.issued2012-12-24en
dc.identifier.issn02767333en
dc.identifier.doi10.1021/om300755jen
dc.identifier.urihttp://hdl.handle.net/10754/562465en
dc.description.abstractDiazaphospholidine-sulfonato Pd(II) complexes [{κ2-P,O-(N- Ar2C2H4N2P)C6H 4SO3}PdMe(L)] 1-L (L = dmso, pyridine, lutidine, or μ-LiCl(solvent); 1a: Ar = Ph, 1b: Ar = 2-MeC6H4, 1c: Ar = 2-MeOC6H4, 1d: Ar = 2,4,6-Me3C 6H2, 1e: Ar = 2,6-iPr2C6H 3, 1f: Ar = 2,6-(p-tolyl)2C6H3) were prepared and structurally characterized. The regioselectivity of methyl acrylate (MA) insertion into the Pd-Me bond is entirely inverted from >93% 1,2-insertion for bulky substituents (1d-f, yielding the insertion products [(P̂O)Pd{κ2-C,O-CH2CHMeC(O)OMe], 12) to the usual electronically controlled 2,1-insertion (>95%) for the less bulky Ar = Ph (1a, yielding the insertion product [(P̂O)Pd{κ2-C,O- CHEtC(O)OMe], 11, and β-H elimination product methyl crotonate). DFT studies underline that this is due to a more favorable insertion transition state (2,1- favored by 12 kJ mol-1 over 1,2- for 1a) vs destabilization of the 2,1-insertion transition state in 1d,e. By contrast, MA insertion into the novel isolated and structurally characterized hydride and deuteride complexes [{κ2-P,O-(N-Ar2C 2H4N2P)C6H4SO 3}PdR(lutidine)] (Ar = 2,6-iPr2C6H3; 9e: R = H, 10e: R = D) occurs 2,1-selectively. This is due to the insertion occurring from the isomer with the P-donor and the olefin in trans arrangement, rather than the insertion into the alkyl from the cis isomer in which the olefin is in proximity to the bulky diazaphospholidine. 1a-f are precursors to active catalysts for ethylene polymerization to highly linear polyethylene with M n up to 35 000 g mol-1. In copolymerization experiments, norbornene was incorporated in up to 6.1 mol % into the polyethylene backbone. © 2012 American Chemical Society.en
dc.description.sponsorshipFinancial support by the DFG (Me1388/10-1) is gratefully acknowledged. The authors thank Lars Bolk for GPC, Anke Friemel and Ulrich Haunz for support with NMR measurements, and the HPC team of Enea (www.enea.it) for use of the ENEA-GRID and the HPC facilities CRESCO (www.cresco.enea.it) in Portici, Italy.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleControlled acrylate insertion regioselectivity in diazaphospholidine- sulfonato palladium(II) complexesen
dc.typeArticleen
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalOrganometallicsen
dc.contributor.institutionDepartment of Chemical Materials Science, University of Konstanz, Universitätsstrasse 10, 78457 Konstanz, Germanyen
dc.contributor.institutionDepartment of Chemistry, University of Salerno, Via Ponte Don Melillo, 84084 Fisciano, Salerno, Italyen
kaust.authorCavallo, Luigien
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