Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

Handle URI:
http://hdl.handle.net/10754/565781
Title:
Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization
Authors:
Liu, Wen; Pan, Weijing; Wang, Peng; Li, Wei; Mu, Jingshan; Weng, Gengsheng; Jia, Xiaoyu; Gong, Dirong; Huang, Kuo-Wei ( 0000-0003-1900-2658 )
Abstract:
Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2’H-benzoimidazole)-2-aminepyridine dichlorocobalt (PN3CoCl2) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively, (PN3 ligand in unit A: (N-di-tert-butylphosphino)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine) with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligandO=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 105g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)
Citation:
Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization 2015 Inorganica Chimica Acta
Publisher:
Elsevier BV
Journal:
Inorganica Chimica Acta
Issue Date:
3-Aug-2015
DOI:
10.1016/j.ica.2015.07.033
Type:
Article
ISSN:
00201693
Is Supplemented By:
Liu, W., Pan, W., Wang, P., Li, W., Mu, J., Weng, G., … Huang, K.-W. (2015). CCDC 1061305: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc14mcns; DOI:10.5517/cc14mcns; HANDLE:http://hdl.handle.net/10754/624430
Additional Links:
http://linkinghub.elsevier.com/retrieve/pii/S0020169315003679
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorLiu, Wenen
dc.contributor.authorPan, Weijingen
dc.contributor.authorWang, Pengen
dc.contributor.authorLi, Weien
dc.contributor.authorMu, Jingshanen
dc.contributor.authorWeng, Gengshengen
dc.contributor.authorJia, Xiaoyuen
dc.contributor.authorGong, Dirongen
dc.contributor.authorHuang, Kuo-Weien
dc.date.accessioned2015-08-10T12:22:54Zen
dc.date.available2015-08-10T12:22:54Zen
dc.date.issued2015-08-03en
dc.identifier.citationSynthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization 2015 Inorganica Chimica Actaen
dc.identifier.issn00201693en
dc.identifier.doi10.1016/j.ica.2015.07.033en
dc.identifier.urihttp://hdl.handle.net/10754/565781en
dc.description.abstractIncomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2’H-benzoimidazole)-2-aminepyridine dichlorocobalt (PN3CoCl2) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively, (PN3 ligand in unit A: (N-di-tert-butylphosphino)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine) with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligandO=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 105g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers.en
dc.language.isoenen
dc.publisherElsevier BVen
dc.relation.urlhttp://linkinghub.elsevier.com/retrieve/pii/S0020169315003679en
dc.rightsNOTICE: this is the author’s version of a work that was accepted for publication in Inorganica Chimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Inorganica Chimica Acta, 3 August 2015. DOI: 10.1016/j.ica.2015.07.033en
dc.subjectco-crystal structureen
dc.subjectCobalt catalysten
dc.subjectPN3 liganden
dc.subjectButadiene polymerizationen
dc.titleSynthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerizationen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalInorganica Chimica Actaen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Polymer Science and Engineering, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. Chinaen
dc.contributor.institutionKey Laboratory of Urban Environment and Health, Institute of Urban Environment, Chinese Academy of Sciences, No.1799, Jimei Road, Xiamen, Fujian 361021, P. R. Chinaen
dc.contributor.institutionNingbo Urban Environment Observation and Research Station-NUEORS, Chinese Academy of Sciences, Ningbo, Zhejiang 315830, P. R. Chinaen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorHuang, Kuo-Weien
dc.relation.isSupplementedByLiu, W., Pan, W., Wang, P., Li, W., Mu, J., Weng, G., … Huang, K.-W. (2015). CCDC 1061305: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc14mcnsen
dc.relation.isSupplementedByDOI:10.5517/cc14mcnsen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624430en
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