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Abstract:
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The Delta-Lambda isomerization of partially resolved [Ni(1,10-phen)(2)(S-aa)](+) systems, where Saa is S-phenylalaninate, S-isoleucinate, S-leucinate, S-valinate, or S-alaninate, has been studied at 15, 20 and 25 degrees C in methanol as solvent. Kinetic parameters have been obtained by means of optical rotation measurements. The first-order rate constants for the isomerization process follow the order S-leu > S-ala > S-phe > S-ileu > S-val, whereas Delta H double dagger and Delta S double dagger are in the sequence S-phe > S-ala > S-val > S-ileu > S-leu. These results are discussed in relation to the possible influences of intramolecular noncovalent interactions on the activation parameters. |