It is shown that model oxides grown on metallic substrates catalyze pr
opylene metathesis to form ethylene and butene with an activity that m
imics that of supported catalysts for reaction below similar to 650 K.
Another reaction regime is found for olefin metathesis above similar
to 650 K, where the reaction proceeds with a much higher activation en
ergy of similar to 60 kcal/mol. Unfortunately, alkenes do not react to
any detecable extent on the model oxide surfaces in ultrahigh vacuum.
However, the high-temperature(> 650 K) metathesis rate is found to be
affected by the presence of oxygen overlayers, which also modify the
chemistry of alkenes on Mo(100) in ultrahigh vacuum. It is found that
methane is formed by reaction of alkenes on O/Mo(100). The only other
products detected are ascribed to either hydrogenation or total therma
l decomposition into carbon and hydrogen. It is shown, using iodine-co
ntaining molecules to graft hydrocarbon fragments onto the surface, th
at alkenes can dissociate, forming carbenes which react to yield metha
ne. This chemistry is in accord with that found catalytically at high
temperatures, where the product distribution from the reaction of ethy
lene is well described by a Schulz-Florey distribution and the product
distribution from propylene is well described by copolymerization of
carbenes and methyl carbenes.