화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.106, No.12, 2855-2861, 2002
Hydrogen deuterium isotope effect on exchange rates in eta(2) bond transition metal dihydrogen complexes revealed by H-2 solid state NMR spectroscopy
A selectively eta(2)-D-2 labeled isotopomer of the complex W(PCy3)(2) (CO)(3)) (eta(2)-D-2) has been synthesized and the H-2 NMR spectra and spin lattice relaxation rates of this complex have been measured in the temperature regime of 50 K to 300 K. The spectra have been analyzed employing a model of a combination of homonuclear dipolar D-D interaction and deuterium quadrupolar interaction and a D-D distance of 0.89 +/- 0.1 Angstrom. The line width of the spectra exhibits a weak temperature dependence at temperatures above 150 K. This temperature dependence is interpreted as a slight decrease of the quadrupolar coupling with increasing temperature, which is an indication of a change of the M-D-2 distance with changing temperatures. The spin lattice relaxation data of the complex exhibit pronounced deviations from a simple Arrhenius behavior at lower temperatures, indicating the presence of a quantum mechanical tunneling process. This process is analyzed in terms of a simple one-dimensional Bell tunnel model. A comparison with INS data from the H-2 complex reveals a strong isotope effect of 2 x 10(3) for the exchange rates of the deuterons.