Regio- and stereo-selective polymerization of 1,3-butadiene catalyzed by phosphorus–nitrogen PN3-pincer cobalt(ii) complexes

Handle URI:
http://hdl.handle.net/10754/622457
Title:
Regio- and stereo-selective polymerization of 1,3-butadiene catalyzed by phosphorus–nitrogen PN3-pincer cobalt(ii) complexes
Authors:
Gong, Dirong; Zhang, Xuequan; Huang, Kuo-Wei ( 0000-0003-1900-2658 )
Abstract:
A new family of cobalt complexes (CoCl2-H, CoCl2-Me, CoCl2-iPr, CoBr2-H, CoBr2-Me, CoBr2-iPr, CoI2-H, CoI2-Me, and CoI2-iPr) supported by a PN3 ligand (6-(N,N′-di-t-butylphosphino)-2-pyrazol-yl-aminopyridine) have been prepared and fully characterized by FT-IR, elemental analysis, and X-ray analysis. The X-ray analysis reveals a trigonal bipyramidal conformation in the solid state for all representative complexes, CoCl2-H, CoBr2-H, CoBr2-iPr and CoI2-Me. The cobalt center is chelated by the PN3 ligand through the pyridinyl nitrogen, the pyrazol nitrogen and the phosphorus donor, with a long Co-P bond distance indicating a labile character. On activation with AlEt2Cl, Al2Et3Cl3, MAO, [Ph3C]+[B(C6F5)4]-/AliBu3 or AliBu3, cis-1,4 selective butadiene polymerization was achieved with up to 98.6% selectivity. The polymerization results show that the cis-1,4 selectivity is influenced by the steric hindrance, increasing with the bulkiness of the substituent groups (CoX2-iPr > CoX2-Me > CoX2-H) at the 3,5-positions of the pyrazole moiety, together with a slight decrease in activity. The activity changes in the order CoCl2L ≈ CoBr2L > CoI2L (for the same ligand L) when MAO is used as the activator, while the high level of cis-1,4 selectivity is maintained. It is possible to switch the selectivity from cis-1,4 to syndiotactic-1,2 by adding PPh3 © The Royal Society of Chemistry.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Gong D, Zhang X, Huang K-W (2016) Regio- and stereo-selective polymerization of 1,3-butadiene catalyzed by phosphorus–nitrogen PN3-pincer cobalt(ii) complexes. Dalton Trans 45: 19399–19407. Available: http://dx.doi.org/10.1039/c6dt03722d.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Dalton Trans.
Issue Date:
11-Nov-2016
DOI:
10.1039/c6dt03722d
Type:
Article
ISSN:
1477-9226; 1477-9234
Sponsors:
The authors thank KAUST for the generous financial support. This work is also supported by the Natural Science Foundation of China (Grant No. 21304050), the Natural Science Foundation of Ningbo (2014A610109) and the Open Research Fund of Key Laboratory of Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (KLSR1501).
Is Supplemented By:
Gong, D., Zhang, X., & Huang, K.-W. (2016). CCDC 1431673: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k1s0d; DOI:10.5517/ccdc.csd.cc1k1s0d; HANDLE:http://hdl.handle.net/10754/624529; Gong, D., Zhang, X., & Huang, K.-W. (2016). CCDC 1431670: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k1rx8; DOI:10.5517/ccdc.csd.cc1k1rx8; HANDLE:http://hdl.handle.net/10754/624526; Gong, D., Zhang, X., & Huang, K.-W. (2016). CCDC 1431671: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k1ry9; DOI:10.5517/ccdc.csd.cc1k1ry9; HANDLE:http://hdl.handle.net/10754/624527; Gong, D., Zhang, X., & Huang, K.-W. (2016). CCDC 1431672: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k1rzb; DOI:10.5517/ccdc.csd.cc1k1rzb; HANDLE:http://hdl.handle.net/10754/624528
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2016/DT/C6DT03722D
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorGong, Dirongen
dc.contributor.authorZhang, Xuequanen
dc.contributor.authorHuang, Kuo-Weien
dc.date.accessioned2017-01-02T09:28:32Z-
dc.date.available2017-01-02T09:28:32Z-
dc.date.issued2016-11-11en
dc.identifier.citationGong D, Zhang X, Huang K-W (2016) Regio- and stereo-selective polymerization of 1,3-butadiene catalyzed by phosphorus–nitrogen PN3-pincer cobalt(ii) complexes. Dalton Trans 45: 19399–19407. Available: http://dx.doi.org/10.1039/c6dt03722d.en
dc.identifier.issn1477-9226en
dc.identifier.issn1477-9234en
dc.identifier.doi10.1039/c6dt03722den
dc.identifier.urihttp://hdl.handle.net/10754/622457-
dc.description.abstractA new family of cobalt complexes (CoCl2-H, CoCl2-Me, CoCl2-iPr, CoBr2-H, CoBr2-Me, CoBr2-iPr, CoI2-H, CoI2-Me, and CoI2-iPr) supported by a PN3 ligand (6-(N,N′-di-t-butylphosphino)-2-pyrazol-yl-aminopyridine) have been prepared and fully characterized by FT-IR, elemental analysis, and X-ray analysis. The X-ray analysis reveals a trigonal bipyramidal conformation in the solid state for all representative complexes, CoCl2-H, CoBr2-H, CoBr2-iPr and CoI2-Me. The cobalt center is chelated by the PN3 ligand through the pyridinyl nitrogen, the pyrazol nitrogen and the phosphorus donor, with a long Co-P bond distance indicating a labile character. On activation with AlEt2Cl, Al2Et3Cl3, MAO, [Ph3C]+[B(C6F5)4]-/AliBu3 or AliBu3, cis-1,4 selective butadiene polymerization was achieved with up to 98.6% selectivity. The polymerization results show that the cis-1,4 selectivity is influenced by the steric hindrance, increasing with the bulkiness of the substituent groups (CoX2-iPr > CoX2-Me > CoX2-H) at the 3,5-positions of the pyrazole moiety, together with a slight decrease in activity. The activity changes in the order CoCl2L ≈ CoBr2L > CoI2L (for the same ligand L) when MAO is used as the activator, while the high level of cis-1,4 selectivity is maintained. It is possible to switch the selectivity from cis-1,4 to syndiotactic-1,2 by adding PPh3 © The Royal Society of Chemistry.en
dc.description.sponsorshipThe authors thank KAUST for the generous financial support. This work is also supported by the Natural Science Foundation of China (Grant No. 21304050), the Natural Science Foundation of Ningbo (2014A610109) and the Open Research Fund of Key Laboratory of Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (KLSR1501).en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2016/DT/C6DT03722Den
dc.titleRegio- and stereo-selective polymerization of 1,3-butadiene catalyzed by phosphorus–nitrogen PN3-pincer cobalt(ii) complexesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalDalton Trans.en
dc.contributor.institutionFaculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Chinaen
dc.contributor.institutionKey Laboratory of Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun, Chinaen
kaust.authorGong, Dirongen
kaust.authorHuang, Kuo-Weien
dc.relation.isSupplementedByGong, D., Zhang, X., & Huang, K.-W. (2016). CCDC 1431673: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k1s0den
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1k1s0den
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624529en
dc.relation.isSupplementedByGong, D., Zhang, X., & Huang, K.-W. (2016). CCDC 1431670: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k1rx8en
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1k1rx8en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624526en
dc.relation.isSupplementedByGong, D., Zhang, X., & Huang, K.-W. (2016). CCDC 1431671: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k1ry9en
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1k1ry9en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624527en
dc.relation.isSupplementedByGong, D., Zhang, X., & Huang, K.-W. (2016). CCDC 1431672: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1k1rzben
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1k1rzben
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624528en
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