Influence of N-Substituents on the Adsorption Geometry of OH-Functionalized Chiral N-Heterocyclic Carbenes

Dery, Shahar; Bellotti, Peter; Ben-Tzvi, Tzipora; Freitag, Matthias; Shahar, Tehila; Cossaro, Albano; Verdini, Alberto; Floreano, Luca; Glorius, Frank; Gross, Elad

Abstract

Adsorption of chiral molecules on heterogeneous catalysts is a simple approach for inducing an asymmetric environment to enable enantioselective reactivity. Although the concept of chiral induction is straightforward, its practical utilization is far from simple, and only a few examples toward the successful chiral induction by surface anchoring of asymmetric modifiers have been demonstrated so far. Elucidating the factors that lead to successful chiral induction is therefore a crucial step for understanding the mechanism by which chirality is transferred. Herein, we identify the adsorption geometry of OH-functionalized N-heterocyclic carbenes (NHCs), which are chemical analogues to chiral modifiers that successfully promoted α-arylation reactions once anchored on Pd nanoparticles. Polarized near-edge X-ray absorption fine structure (NEXAFS) measurements on Pd(111) revealed that NHCs that were associated with low enantioselectivity were characterized with a well-ordered structure, in which the imidazole ring was vertically positioned and the OH-functionalized side arms were flat-lying. OH-functionalized NHCs that were associated with high enantioselectivity revealed a disordered/flexible adsorption geometry, which potentially enabled better interaction between the OH group and the prochiral reactant.