Acetylene coupling on Cu(111): formation of butadiene, benzene, and cyclooctatetraene.
Acetylene trimerizes to benzene on the (111) face of copper, as it does on the (100) and (110) planes. However, Cu(111) also yields butadiene and cyclooctatetraene, the latter never previously found with Cu or any other material. No coverage threshold is observed for the onset of these coupling reactions, implying high adsorbate mobility: gaseous benzene is formed by a surface reaction rate-limited process, whereas butadiene and cyclooctatetraene are formed by desorption rate-limited processes. H/D isotope tracing shows that benzene formation proceeds via a statistically random associative mechanism, whereas butadiene formation is associated with strong kinetic isotope effects, probably associated with C-H cleavage. A pericyclic mechanism involving dimerization of C4H4 metallocycles is proposed to account for the formation of cyclooctatetraene. We also found that approximately 45 nm alpha-alumina supported copper particles operated under catalytic conditions at atmospheric pressure yield the same principal reaction products as those found with Cu(111) under vacuum conditions. It therefore seems likely that the elementary reaction steps that describe the surface chemistry of the model system are also important under practical conditions. Comparison of the structure, bonding, and reactivity of acetylene on Cu(111) and Pd(111) indicates that the effectiveness of copper in promoting C-H cleavage in adsorbed acetylene is associated with greater rehybridization of the C-C bond with concomitant weakening of the C-H bond.
Kyriakou
Georgios
G
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom.
Kim
Jisu
J
Tikhov
Mintcho S
MS
Macleod
Norman
N
Lambert
Richard M
RM