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http://hdl.handle.net/2445/127695
Title: | Ligand sequential replacement on chromium(III)-aqua complexes by L-alanine and other biological amino acids: a kinetic perspective |
Author: | Pérez de Benito, Joaquín F. Martínez Cereza, Guillem |
Keywords: | Crom Cinètica química Aminoàcids Chromium Chemical kinetics Amino acids |
Issue Date: | 17-Sep-2018 |
Publisher: | American Chemical Society |
Abstract: | The ligand sequential replacement on chromium(III)-aqua complexes by L-alanine in slightly acidic aqueous solutions (pH range: 3.55-5.61) has been kinetically followed by means of UV-Vis spectrophotometry. A two rate constant model has been applied to fit the absorbance-time data, corresponding to the formation (k1) and decay (k2) of an intermediate not reactive enough to be in steady state (long-lived intermediate). The kinetic orders of the amino acid were fractional (0.40 ± 0.03 for k1 and 0.40 ± 0.02 for k2). The two steps showed base catalysis, and the activation energies were 60 ± 3 (for k1) and 83 ± 6 (for k2) kJ mol-1. The rate constants for the coordination of the first L-alanine ligand followed the sequence CrOH2+ < Cr(OH)2+ < Cr(OH)3, Cr3+ being almost inactive. This suggests that the increase in the reaction rate with increasing pH was caused by the enhancement of the lability of the Cr(III)-aqua bonds induced by the presence of hydroxo ligands. The activation parameters for a series of ligand substitution on Cr(III)-aqua complexes by organic molecules yielded a statistically significant enthalpy-entropy linear plot with an isokinetic temperature of 296 ± 21 K. |
Note: | Versió postprint del document publicat a: https://doi.org/10.1021/acs.jpca.8b07824 |
It is part of: | Journal of Physical Chemistry A, 2018, vol. 122, num. 40, p. 7962-7973 |
URI: | http://hdl.handle.net/2445/127695 |
Related resource: | https://doi.org/10.1021/acs.jpca.8b07824 |
ISSN: | 1089-5639 |
Appears in Collections: | Articles publicats en revistes (Ciència dels Materials i Química Física) |
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