| Sumario: | Unprecedented surface chemistry, governed by specific atomic arrangements and the steric effect of ordered alloys, is reported. Rh-based ordered alloys supported on SiO (RhM/SiO, M = Bi, Cu, Fe, Ga, In, Pb, Sn, and Zn) were prepared and tested as catalysts for selective hydrogenation of trans-1,4-hexadiene to trans-2-hexene. RhBi/SiO exhibited excellent regioselectivity for the terminal C═C bond and chemoselective hydrogenation to the monoene, not to the overhydrogenated alkane, resulting in a high trans-2-hexene yield. Various asymmetric dienes, including terpenoids, were converted into the corresponding inner monoenes in high yields. This is the first example of a regio- and chemoselective hydrogenation of dienes using heterogeneous catalysts. Kinetic studies and density functional theory calculations revealed the origin of the high selectivity: (1) one-dimensionally aligned Rh arrays geometrically limit hydrogen diffusion and attack to alkenyl carbons from one direction and (2) adsorption of the inner C═C moiety to Rh is inhibited by steric repulsion from the large Bi atoms. The combination of these effects preferentially hydrogenates the terminal C═C bond and prevents overhydrogenation to the alkane.
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