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Metal-to-Metal Distance Modulated Au(I)/Ru(II) Cyclophanyl Complexes: Cooperative Effects in Photoredox Catalysis |
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| Authors: | Christoph Zippel Roumany Israil Lars Schüssler Dr Zahid Hassan Erik K Schneider Dr Patrick Weis Dr Martin Nieger Dr Claudia Bizzarri Prof?Dr Manfred M Kappes Dr Christoph Riehn Prof?Dr Rolf Diller Prof?Dr Stefan Bräse |
| Institution: | 1. Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany;2. Department of Chemistry, Technische Universität Kaiserslautern (TUK), Erwin-Schrödinger-Str. 52, 67663 Kaiserslautern, Germany;3. Department of Physics, Technische Universität Kaiserslautern (TUK), Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany;4. Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber Weg 2, 76131 Karlsruhe, Germany;5. Department of Chemistry, University of Helsinki, P. O. Box 55, Helsinki, 00014 Finland;6. Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber Weg 2, 76131 Karlsruhe, Germany
Institute of Nanotechnology, Karlsruhe Institute of Technology, Herman-von Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany;7. Department of Chemistry, Technische Universität Kaiserslautern (TUK), Erwin-Schrödinger-Str. 52, 67663 Kaiserslautern, Germany Research Center OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern, Germany |
| 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. |
| Keywords: | metal-to-metal distance modulation heterometallic complexes cooperative effects photoredox catalysis [2 2]paracyclophane gold ruthenium |