Stepwise or Concerted Addition of 1,3-Butadiene to Oxygen Adsorbed on the Ag(110) Surface?

Article abstract of DOI:10.1021/j100143a036

The interaction of 1,3-butadiene with atomically adsorbed oxygen on a Ag(110) surface is studied.Three different approaches of 1,3-butadiene to an oxygen atom that is adsorbed in the two-fold bridging site of the grooves on the Ag(110) surface are studied: a cheletropic 1,4-cycloaddition, an interaction with the terminal carbon, and an interaction with the internal carbon of the 1,3-butadiene.Extended Hueckel tight-binding calculations show that the interaction of one of the terminal carbons of 1,3-butadiene with the surface oxygen is favored.This intermediate shows a preference for a 1,4 ring closure reaction rather than a 1,2 ring closure reaction, leading to 2,5-dihydrofurane instead of vinyl epoxide.The interaction between the suggested intermediates and the Ag(110) surface as well as the bonding of different adsorbed products are analyzed and discussed in relation to the experimental results.