Synthesis of bis(N-arylcarboximidoylchloride)pyridine cobalt(ii) complexes and their catalytic behavior for 1,3-butadiene polymerizationElectronic supplementary information (ESI) available. CCDC 872215, 903515, 903516, 903517, 941866 and 941867. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3dt51403j
A new family of bis( N -arylcarboximidoylchloride)pyridine cobalt( ii ) complexes with the general formula [2,6-(ArN&z.dbd;CCl) 2 C 5 H 3 N]CoCl 2 (Ar = 2,4,6-Me 3 C 6 H 2 , 4a ; 2,6- i Pr 2 C 6 H 3 , 4b ; 2,6-Me 2 C 6 H 3 , 4c ; C 6 H 5 , 4d ; 4-Cl-2,6-Me 2 C 6 H 2 , 4e ) and a typical Brookhar...
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Main Authors | , , , , , , , , , , |
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Format | Journal Article |
Language | English |
Published |
27.08.2013
|
Online Access | Get full text |
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Summary: | A new family of bis(
N
-arylcarboximidoylchloride)pyridine cobalt(
ii
) complexes with the general formula [2,6-(ArN&z.dbd;CCl)
2
C
5
H
3
N]CoCl
2
(Ar = 2,4,6-Me
3
C
6
H
2
,
4a
; 2,6-
i
Pr
2
C
6
H
3
,
4b
; 2,6-Me
2
C
6
H
3
,
4c
; C
6
H
5
,
4d
; 4-Cl-2,6-Me
2
C
6
H
2
,
4e
) and a typical Brookhart-Gibson-type reference complex [2,6-(2,4,6-Me
3
C
6
H
2
N&z.dbd;CMe)
2
C
5
H
3
N]CoCl
2
(
5a
) were synthesized and characterized. Determined by X-ray crystallographic analysis, complexes
4a
,
4c-e
, and
5a
adopted a trigonal bipyramidal configuration, and
4b
adopted a distorted square pyramidal geometry. In combination with ethylaluminum sesquichloride (EASC), all the complexes were highly active towards 1,3-butadiene polymerization, affording polybutadiene with predominant
cis
-1,4 content (up to 96%).
4a
with chlorine atoms at the imine groups exhibited higher catalytic activity than did
5a
, indicating that the incorporation of chlorine atoms into the ligand improves the activity. The activity of the complexes in 1,3-butadiene polymerization was in the order of
4a
>
4c
∼
4e
∼
4b
>
4d
, which is consistent with the trend of spatial opening degree around the metal center in the complexes as revealed by crystallographic data. Screening polymerization conditions proved that EASC was the most efficient among the cocatalysts examined.
Bis(
N
-arylcarboximidoylchloride)pyridine cobalt(
ii
) complexes catalyze 1,3-butadiene polymerization with a high
cis
-1,4-selectivity and perform a higher activity than the Brookhart-Gibson-type complex. |
---|---|
Bibliography: | Electronic supplementary information (ESI) available. CCDC For ESI and crystallographic data in CIF or other electronic format see DOI and 10.1039/c3dt51403j 941866 941867 , 903515 872215 903516 903517 |
ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c3dt51403j |