Inorganic Chemistry, volume 48, issue 7, pages 2830-2836
Binding of 4-(N,N-dimethylamino)pyridine to Salen- and Salan-Cr(III) Cations: A Mechanistic Understanding on the Difference in Their Catalytic Activity for CO2/Epoxide Copolymerization
Publication type: Journal Article
Publication date: 2009-03-09
Journal:
Inorganic Chemistry
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 4.6
ISSN: 00201669, 1520510X
Inorganic Chemistry
Physical and Theoretical Chemistry
Abstract
The coordination chemistry of 4-(N,N-dimethylamino)pyridine (DMAP) with Salen- or Salan- (where the tetradentate N,N'-disubstituted bisaminophenoxide is designated as Salan, a saturated version of the Schiff-base Salen ligand) chromium complexes was studied by electrospray ionization mass spectrometry (ESI-MS). The relative stabilities of mono DMAP adducts of these chromium complexes were characterized by collision-induced dissociation (CID) and further discussed with regard to the activity in catalyzing CO(2)/epoxide copolymerization. [SalenCr](+) cations preferably bind two DMAP molecules to form six-coordinated complex ions, while [SalanCr](+) cations usually bind one molecule of DMAP to form five-coordinated complex ions, which were found to be relatively unstable. The remarkable difference in the coordination of DMAP to these two chromium complexes resulted in a significant difference in catalytic activity for the alternating copolymerization of CO(2) and propylene oxide. In the presence of 1 equiv of DMAP, the activity of the chromium-Salan complex 2a was up to 86 h(-1) of TOF at ambient temperature, which was about 30 times that of the corresponding chromium-Salen complex 1a. In sharp contrast to a long induction period up to 2 h with the use of 1a in conjunction with DMAP as catalyst, no initiation time or a very short one was observed in the binary 2a/DMAP catalyst systems. The initiator role of DMAP was confirmed by continuous determination of the propagating polymer species at various intervals using ESI-MS, which in combination with a kinetic study by means of infrared spectroscopy resulted in a mechanistic understanding on the difference in activity of the two catalyst systems for CO(2)/epoxide copolymerization.
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- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
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Rao D. Y. et al. Binding of 4-(N,N-dimethylamino)pyridine to Salen- and Salan-Cr(III) Cations: A Mechanistic Understanding on the Difference in Their Catalytic Activity for CO2/Epoxide Copolymerization // Inorganic Chemistry. 2009. Vol. 48. No. 7. pp. 2830-2836.
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Rao D. Y., Li B., Zhang R., Wang H., Lu X. Binding of 4-(N,N-dimethylamino)pyridine to Salen- and Salan-Cr(III) Cations: A Mechanistic Understanding on the Difference in Their Catalytic Activity for CO2/Epoxide Copolymerization // Inorganic Chemistry. 2009. Vol. 48. No. 7. pp. 2830-2836.
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TY - JOUR
DO - 10.1021/ic802384x
UR - https://doi.org/10.1021/ic802384x
TI - Binding of 4-(N,N-dimethylamino)pyridine to Salen- and Salan-Cr(III) Cations: A Mechanistic Understanding on the Difference in Their Catalytic Activity for CO2/Epoxide Copolymerization
T2 - Inorganic Chemistry
AU - Rao, Dun Yan
AU - Li, Bo
AU - Zhang, Rong
AU - Wang, Hui
AU - Lu, Xiao-Bing
PY - 2009
DA - 2009/03/09 00:00:00
PB - American Chemical Society (ACS)
SP - 2830-2836
IS - 7
VL - 48
SN - 0020-1669
SN - 1520-510X
ER -
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@article{2009_Rao,
author = {Dun Yan Rao and Bo Li and Rong Zhang and Hui Wang and Xiao-Bing Lu},
title = {Binding of 4-(N,N-dimethylamino)pyridine to Salen- and Salan-Cr(III) Cations: A Mechanistic Understanding on the Difference in Their Catalytic Activity for CO2/Epoxide Copolymerization},
journal = {Inorganic Chemistry},
year = {2009},
volume = {48},
publisher = {American Chemical Society (ACS)},
month = {mar},
url = {https://doi.org/10.1021/ic802384x},
number = {7},
pages = {2830--2836},
doi = {10.1021/ic802384x}
}
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Rao, Dun Yan, et al. “Binding of 4-(N,N-dimethylamino)pyridine to Salen- and Salan-Cr(III) Cations: A Mechanistic Understanding on the Difference in Their Catalytic Activity for CO2/Epoxide Copolymerization.” Inorganic Chemistry, vol. 48, no. 7, Mar. 2009, pp. 2830-2836. https://doi.org/10.1021/ic802384x.