Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 42, Pages 15222-15231Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b09079
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Funding
- Center for Sustainable Polymers, an NSF Center for Chemical Innovation [CHE-1413862]
- NSF [CHE-1531632]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1413862] Funding Source: National Science Foundation
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Mechanistic studies involving synergistic experiment and theory were performed on the perfectly alternating copolymerization of 1-butene oxide and carbic anhydride using a (salph)AlCl/[PPN]Cl catalytic pair. These studies showed a first-order dependence of the polymerization rate on the epoxide, a zero-order dependence on the cyclic anhydride, and a LLI first-order dependence on the catalyst only if the two members of the catalytic pair are treated as a single unit. Studies of model complexes showed that a mixed alkoxide/carboxylate aluminum intermediate preferentially opens cyclic anhydride over epoxide. In addition, ring-opening of epoxide by an intermediate comprising multiple carboxylates was found to be rate determining. On the basis of the experimental results and analysis by DFT calculations, a mechanism involving two catalytic cycles is proposed wherein the alternating copolymerization proceeds via intermediates that have carboxylate ligation in common, and a secondary cycle involving a bis-alkoxide species is avoided, thus explaining the lack of side reactions until the polymerization is complete.
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