Metal‐to‐Metal Distance Modulated Au(I)/Ru(II) Cyclophanyl Complexes: Cooperative Effects in Photoredox Catalysis. Issue 61 (28th October 2021)

• Record Type: Journal Article
• Authors: Zippel, Christoph; Israil, Roumany; Schüssler, Lars; Hassan, Zahid; Schneider, Erik K.; Weis, Patrick; Nieger, Martin; Bizzarri, Claudia; Kappes, Manfred M.; Riehn, Christoph; Diller, Rolf; Bräse, Stefan
• Is Part Of: Chemistry. Volume 27:Issue 61(2021)
• Page Start: 15188
• Page End: 15201
• Publication Date: 2021-10-28
• Subjects: metal-to-metal distance modulation -- heterometallic complexes -- cooperative effects -- photoredox catalysis -- [2.2]paracyclophane -- gold -- ruthenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202102341
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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. The 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. Abstract : 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.