Acceleration and deceleration of chirality inversion speeds in a dynamic helical metallocryptand by alkali metal ion...

We report that the chirality inversion kinetics of a trinickel(II) cryptand can be controlled by guest recognition in the cryptand cavity. When the guest was absent, the nickel(II) cryptand underwent a dynamic interconversion between the P and M forms in solution, preferring the M form, with a half-life of t_1/2 = 4.99 min. The P/M equilibrium is reversed to P-favored by binding with an alkali metal ion in the cryptand cavity. The timescale of this M→P inversion kinetics was both notably accelerated and decelerated by the guest binding (t_1/2 = 0.182 min for K⁺ complex; 186 min for Cs⁺ complex); thus, the equilibration rate constants differed by up to 1000-fold depending on the guest metal ions. This acceleration/deceleration can be explained in terms of the virtual binding constants at the transition state of the P/M chirality inversion; K⁺ binding more stabilizes the transition state rather than the P and M forms to result in the acceleration.