Metal-to-Metal Distance Modulated Au(I)/Ru(II) Cyclophanyl Complexes: Cooperative Effects in Photoredox Catalysis

M-to-M Distance Modulation: Au(I)/Ru(II) decorated mono- and distance-modulated heterobimetallic complexes featuring co-facially stacked π-conjugated [2.2]paracyclophanes as rigid spacer are synthesized. Employing a broad set of architectural arrangements of cyclophanyl-derived pseudo-geminal, -ortho, -meta, and -para substitution patterns, enables metal-to-metal distance modulation with defined spatial orientation of the Au(I)/Ru(II) metal centers. The Au(I)/Ru(II) heterobimetallic complexes with varying metal-to-metal distances provide a promising platform for the investigation of structure, property, and reactivity relation in cooperative effects.

The modular synthesis of Au(I)/Ru(II) decorated mono- and heterobimetallic complexes with π-conjugated [2.2]paracyclophane is described. [2.2]Paracyclophane serves as a rigid spacer which holds the metal centers in precise spatial orientations and allows metal-to-metal distance modulation. A broad set of architectural arrangements of pseudo -geminal, -ortho, -meta, and -para substitution patterns were employed. Metal-to-metal distance modulation of Au(I)/Ru(II) heterobimetallic complexes and the innate transannular π-communication of the cyclophanyl scaffold provides a promising platform for the investigations of structure-activity relationship and cooperative effects. ... mehrThe Au(I)/Ru(II) heterobimetallic cyclophanyl complexes are stable, easily accessible, and exhibit promising catalytic activity in the visible-light promoted arylative Meyer-Schuster rearrangement.