Pyridine, the quinolines,
pyridazine, pyrimidine, pyrazine, s-triazine, and
aniline have been exchanged with heavy water on the following Group VIII
transition metals: Fe, Co, Ni, 0s. Ru, Rh, Pd, Ir,
and Pt. Three types of catalyst activation have been used, including
self-activation, hydrogen and sodium borohydride reduction of the inorganlo salts. Platinum is the most useful catalyst for
general exchange whereas cobalt possesses valuable specificity for selective a
exchange in a large number of the heterocyclic compounds. A kinetic study of
the deuteration of pyridine on platinum has been
performed. The exchange results have been rationalized in terms of
charge-transfer adsorbed intermediates. E.s.r. has been used to support this
conclusion for the interaction between pyridine and potassium chloropalladite. π-Complex mechanisms have been
proposed to explain the observed deuteration
behaviour.
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