Journal
RSC ADVANCES
Volume 4, Issue 79, Pages 41848-41855Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4ra05455e
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Funding
- National Natural Science Foundation of China [21074097, 21274112]
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Kinetic studies of the carbene polymerization of ethyl diazoacetate (EDA) by palladium (Pd) or rhodium (Rh) catalysts were investigated by real-time Fourier transform infrared (FTIR) spectroscopy. Both (L-prolinate) Rh-I(1,5-cyclooctadiene) and (L-prolinate) Rh-I(2,5-norbornadiene) mediated EDA polymerization were proved to be first order reactions, suggesting that the formation of Rh-carbenoid is the rate determining step. The activation energy (11.24 kJ mol(-1)) of the polymerization of carbenes generated from EDA with (L-prolinate) RhI(1,5-cyclooctadiene) as the catalyst was calculated from kinetic data via the Arrhenius equation. On the other hand, the polymerizations of EDA catalyzed by three kinds of Pd-catalysts were revealed as zero order reactions, suggesting that the rate determining step involves the formation of an EDA-Pd transition state complex through a coordinated step. Refilling more EDA to the (bis(acetonitrile) dichloropalladium)-mediated carbene polymerization system did not change the reaction order. The rate constant increases gradually with the increase of the dosage of the catalyst and decreases with the cycle-index, which proves the formation of EDA-Pd transition state complex and the propagating species with Pd-C bonds at the end of the polymer chain.
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