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See Supporting Information.
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2 addition may also influence the rate of conversion to 4, obscuring firm conclusions regarding inhibition by dinitrogen.
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2 addition may also influence the rate of conversion to 4, obscuring firm conclusions regarding inhibition by dinitrogen.
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Less than 15% formation of 2 was observed prior to complete conversion of 1 to 4.
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Less than 15% formation of 2 was observed prior to complete conversion of 1 to 4.
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The C-C bond forming event may also be viewed as a nucleophilic attack by ethylene on the electrophilic carbon dioxide.
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The C-C bond forming event may also be viewed as a nucleophilic attack by ethylene on the electrophilic carbon dioxide.
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A third possibility, rate-limiting dimerization, is deemed unlikely given that the absence of observable acrylate hydride monomer necessitates two rapid equilibria between 4-metallalactone and metallalactone-acylate hydride monomer, both of which must favor the reactants. This possibility is also excluded on the basis of the measured KIE and activation entropy.
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A third possibility, rate-limiting dimerization, is deemed unlikely given that the absence of observable acrylate hydride monomer necessitates two rapid equilibria between 4-metallalactone and metallalactone-acylate hydride monomer, both of which must favor the reactants. This possibility is also excluded on the basis of the measured KIE and activation entropy.
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