Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO2 Fixations

Abstract Unique self‐assembled macrocyclic multinuclear Zn II and Ni II complexes with binaphthyl‐bipyridyl ligands (L) were synthesized. X‐ray analysis revealed that these complexes consisted of an outer ring (Zn 3 L 3 or Ni 3 L 3 ) and an inner core (Zn 2 or Ni). In the Zn II complex, the inner Zn 2 part rotated rapidly inside the outer ring in solution on an NMR timescale. These complexes exhibited dual catalytic activities for CO 2 fixations: synthesis of cyclic carbonates from epoxides and CO 2 and temperature‐switched N ‐formylation/ N ‐methylation of amines with CO 2 and hydrosilane.