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.
|Original language||English (US)|
|Number of pages||7|
|Journal||Inorganica Chimica Acta|
|State||Published - Aug 5 2015|
Bibliographical noteKAUST Repository Item: Exported on 2020-10-01
ASJC Scopus subject areas
- Materials Chemistry
- Physical and Theoretical Chemistry
- Inorganic Chemistry
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CCDC 1061305: Experimental Crystal Structure Determination : Dichloro-(P,P-di-t-butyl-N-(6-(1-methyl-1H-benzimidazol-2-yl)pyridin-2-yl)phosphinous amide)-cobalt dichloro-(P,P-di-t-butyl-N-(6-(1-methyl-1H-benzimidazol-2-yl)pyridin-2-yl)phosphinic amide)-(di
Liu, W. (Creator), Pan, W. (Creator), Wang, P. (Creator), Li, W. (Creator), Mu, J. (Creator), Weng, G. (Creator), Jia, X. (Creator), Gong, D. (Creator), Huang, K. (Creator), Liu, W. (Creator), Pan, W. (Creator), Li, W. (Creator), Mu, J. (Creator), Weng, G. (Creator), Jia, X. (Creator) & Gong, D. (Creator), Cambridge Crystallographic Data Centre, Apr 23 2015
DOI: 10.5517/cc14mcns, http://hdl.handle.net/10754/624430