Broadening the catalytic region from the cavity to windows by M₆L₁₂ nanospheres in cyclizations

Abstract

M6L12 nanospheres, with isolated gold sites fixed on the windows, were utilized as an example to prove that the cage windows present a confinement effect for substrate pre-organization and transition state stabilization leading to high rates.

Orientational Self-Sorting in Octahedral Palladium Cages: Scope and Limitations of the “cis Rule”

“…4 Since then, numerous other [Pd 6 L 12 ] 12+ cages have been described 5−17 and applications were explored (e.g., molecular recognition of dyes 14 and fullerenes; 15 catalysis). 16 Nearly all [Pd 6 L 12 ] 12+ cages reported to date are based on homoditopic ligands, i.e., ligands with two identical N-donor groups. As a consequence, these [Pd 6 L 12 ] 12+ assemblies display high apparent symmetry in solution.…”

“…The first example of a [Pd 6 L 12 ] 12+ cage was presented in the year 2009 by the group of Fujita . Since then, numerous other [Pd 6 L 12 ] 12+ cages have been described − and applications were explored (e.g., molecular recognition of dyes and fullerenes; catalysis) . Nearly all [Pd 6 L 12 ] 12+ cages reported to date are based on homoditopic ligands, i.e., ligands with two identical N-donor groups.…”