Clean gold surface is inactive toward H2.1 Continuing our effort to computationally design molecular structures to active H2,2 we herein present a computational finding that gold surface could serve as a Lewis acid coupling with Lewis bases (e.g. imine and nitrile) to construct effective frustrated Lewis pairs (FLPs3) to activate H2 and subsequently to achieve hydrogenation of small imine and nitrile.4 The Lewis base-coupled Au FLPs utilize the synergetic catalytic effects of Lewis acids and bases to achieve high reactivity toward H2, but distinguish from the normal FLPs in the four aspects: a)  Instead of using bulky substituents or molecular skeletons to prevent the formation of stable Lewis acid/base adducts by normal FLPs, the Lewis base-coupled Au FLPs avoid tight adsorption by using the repulsion between N lone pair and the filled d-band electrons of gold surface; b)  except for the Lewis basic effect of ammonia/imine/nitrile, the Au dz2 state also donates electron to H2 s*-antibonding orbital, but the net effect of Au surface plays a role as a Lewis acid; c )  instead of using localized Lewis acid site in normal FLPs, it uses the partially filled s- and p-band to accept the electrons from the H2 bonding s orbital; d)  among Cu, Ag, and Au surfaces, Au surfaces exhibit such reactivity most significantly, because Au is much more electronegative than Cu and Ag. The study enriches the FLP chemistry by adding a new type (heterogeneous) of FLPs and reveals a new reaction mode for gold surface.References:1.  Hammer, B.; N�rskov, Nature, J. K. 1995, 376 , 238.2. Wang, Z.-X.; Zhao, L.; Lu, G.; Li, H.; Huang, F. Top. Curr. Chem. 2013, 332 , 231.3. (a) Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed., 2010, 49 , 46. (b) Stephan, D. W. Org. Biomol. Chem., 2012, 10 , 5740.4. Lu, G.; Zhang, P. ; Sun, D.; Wang, L.; Zhou, K.; Wang, Z-X.; Guo K. 2014,5  , 1082

Enhanced reactivity of Au surface toward H<sub>2</sub> via collaboration with a Lewis base: Lewis base-coupled gold FLP

248th National Meeting (2014)

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Enhanced reactivity of Au surface toward H2 via collaboration with a Lewis base: Lewis base-coupled gold FLP

Enhanced reactivity of Au surface toward H₂ via collaboration with a Lewis base: Lewis base-coupled gold FLP