Simultaneous determination of structural and kinetic parameters characterizing the interconversion of highly dispersed species: the interaction of NO with Rh-I(CO)(2)/gamma-Al2O3

Newton, Mark A., Burnaby, Daryl G., Dent, Andrew J., Diaz-Moreno, Sofia, Evans, John, Fiddy, Steven G., Neisius, Thomas, Pascarelli, Sakura and Turin, Sandra (2001) Simultaneous determination of structural and kinetic parameters characterizing the interconversion of highly dispersed species: the interaction of NO with Rh-I(CO)(2)/gamma-Al2O3. Journal of Physical Chemistry A, 105 (25), 5965-5970. (doi:10.1021/jp011621x).

Abstract

Energy-dispersive EXAFS (EDE), combined with mass spectrometry and a flow microreactor system, has been used to investigate the reaction of an Al2O3-supported Rh-I(CO)(2) species with NO. This combined in situ approach uniquely permits a priori analysis of the structures of the species involved (on a time scale of ca. 2 s) and simultaneous determination of reaction mechanism and kinetic parameters. In the current case, it is found that the Al(O)Rh-I(CO)(2)Cl species reacts to form an intermediate Al(O)Rh(NO)(2)Cl Cl species (v approximate to 0.357 +/- 0.125 s(-1), E-act approximate to 11 +/- 1.25 kJ mol(-1)), which subsequently forms an (AlO)(2)Rh(NO)Cl- species and N2O(g) (v approximate to 2 +/- 0.5 x 10(4) s(-1), E-act approximate to 40 +/- 3.5 kJ mol(-1)) showing a bent (134 degrees) RhNO bond. This combination of rapid and complementary techniques should be applicable to a wide range of disciplines where quantitative structural and kinetic determinations are of importance.

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