Rate Constants and Thermodynamic Parameters of Rotation of Axial Ligands in a Bisligated Ferric Tetramesitylporphyrinate Complex Measured from the Temperature Dependence of 1H Transverse Relaxation Rates
Momot, Konstantin I. & Walker, F. Ann (1998) Rate Constants and Thermodynamic Parameters of Rotation of Axial Ligands in a Bisligated Ferric Tetramesitylporphyrinate Complex Measured from the Temperature Dependence of 1H Transverse Relaxation Rates. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 102, pp. 10682-10688.
The rate constant of the four-site cyclic chemical exchange between pyrrole protons in tetramesitylporphyrinatoiron(III)bis(2-methylimidazole) has been measured in the temperature range 236-255 K from 1H transverse relaxation times (T2) observed at the 500 MHz field strength. The values of the rate constant were obtained through the simulation of the observed T2’s under the assumption that their values are dominated by the rate of the chemical exchange. The measurement of the exchange rate constant was also attempted at a lower temperature (230 K), but the use of extrapolated intrinsic T2’s at that temperature introduces a significant error into the simulated rate constant. The thermodynamic activation parameters of the cyclic exchange were determined as ¢Hq ) 48 ( 1 kJ/mol and ¢Sq ) -10 ( 6 J/Kâmol. The value of k varied from 30 to 270 s-1 in the temperature range 236-255 K. The near-zero exchange activation entropy is consistent with two previous studies but contradicts another study based on saturation-transfer measurements previously carried out by the authors of this work. A comparison of all available studies shows that the saturation-transfer experiments overestimate the value of the exchange rate constant by up to a factor of 2. It is shown that equilibrium with the high-spin form of the porphyrin complex does not affect the observed T2's in the temperature range used in this study but may do so at temperatures above 270 K. It is also shown that neither the linearity of the Curie plot nor the behavior of the T1 versus temperature plot should be considered indicators of the absence of the low-spin h high-spin equilibrium.
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|Item Type:||Journal Article|
|Additional Information:||This article is freely available from the American Chemical Society website 12 months after the publication date. See links to publisher website in this record.|
|Subjects:||Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600) > Physical Chemistry not elsewhere classified (030699)|
|Divisions:||Past > QUT Faculties & Divisions > Faculty of Science and Technology|
|Copyright Owner:||Copyright 1998 American Chemical Society|
|Copyright Statement:||The contents of this journal can be freely accessed online via the ACS web page 12 months after publication. See link to ACS website.|
|Deposited On:||24 Nov 2008|
|Last Modified:||20 Apr 2015 05:00|
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