Dynamically Bifurcating Hydride Transfer Mechanism and Origin of Inverse Isotope Effect for Heterodinuclear AgRu-Catalyzed Alkyne Semihydrogenation

Abstract

The mechanism and heterodinuclear cooperative effects for AgRu-catalyzed alkyne semihydrogenation were analyzed with density-functional theory (DFT) and experiment. This combined effort revealed the following: (1) AgRu-catalyzed diphenylacetylene hydrogenation initially gives a kinetic mixture of cis-stilbene and trans-stilbene by an ionic Ag–H hydride transfer transition state and post-transition state bifurcation, which was identified by quasiclassical direct dynamics simulations. (2) The hydrogenation reaction exhibits an unexpected inverse kinetic isotope effect (KIE < 1) resulting from an inverse equilibrium isotope effect (EIE) for heterodinuclear H2/D2 activation. (3) The Ag–Ru heterodinuclear cooperative effective is critical for both H2 activation and vinylsilver protonolysis reaction steps. (4) Rate studies and computational analysis show that electron-donating groups accelerate catalysis.