ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The rate law for the demetallation of the title indium(III)-porphin complex in aqueous acidic thiocyanate media at 3.00M ionic strength was found to be of the form \documentclass{article}\pagestyle{empty}\begin{document}$$+ \frac{{d{\rm [H}_{\rm 4} {\rm P}^{{\rm 2} - } {\rm]}}}{{dt}} = \frac{{ab[{\rm H}^{\rm + }]^2 [{\rm NCS}^ -]^2 }}{{1 + b[{\rm H}^{\rm + }]^2 }}[{\rm InP]}_{\rm t}$$\end{document} where [H4P2-] is the concentration of the diacid product formed, [InP]t is the total concentration of all forms of indium(III)-porphin complex present, and a and b are constants. The constant a is a pseudo-third-order rate constant with the value (0.057 ± 0.005)M-2 s-1 and b has the value 0.704M-2 at 50.5°C. If the mechanism for demetallation involves ringpuckering with the attachment of two H+ ions, then 1/b can be identified with the product K1K2 for the stepwise dissociation of two protons from two ring pyrrolic nitrogen atoms of H2InP-. In the sulfonated tetraphenylporphin used for these studies the ring pyrrolic nitrogen atoms seem to be the most probable sites for protonation. If this identification is correct, the value of 1.42 ± 0.13 found for the product K1K2 shows the enormous effect that the presence of the In3+ center has on the ionization constants of these two protons. That the kinetic studies show saturation effects with respect to proton addition to InP3- may result from the fact that In3+ sits about 0.6 Å above the porphin ring.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550140805
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