Kinetics evidence for a complex between peroxynitrous acid and titanium(IV) |
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Authors: | Wick Patrick K Kissner Reinhard Koppenol Willem H |
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Institution: | Laboratorium für Anorganische Chemie, Departement Chemie und Angewandte Biowissenschaften, ETH H?nggerberg, HCI H211, CH-8093 Zürich, Switzerland. |
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Abstract: | The reaction between TiO(2+) and ONOOH in 0.9 M H(2)SO(4) provides evidence for direct formation, previously unobserved, of a HOONO-metal complex. The reaction proceeds via formation of an end-on complex (k = 3.0 x 10(2) M(-1) s(-1)) that rearranges to form a side-on complex (k approximately equal to 20 s(-1)). With ONOOH in excess, this rearrangement proceeds more slowly (k approximately equal to 0.1 s(-1)), probably because multiple hydrogen oxoperoxonitrate molecules form end-on complexes with oxotitanium(IV) and hinder rearrangement to the side-on complex. The absorption spectrum of the final product is that of TiO(2)(2+). Presumably, during the rearrangement or later, NO+ is lost. |
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