Heterobimetallic Cuprates Consisting of a Redox‐Switchable,Silicon‐Based Metalloligand: Synthesis,Structures, and Electronic Properties |
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Authors: | Dipl.‐Chem. Steffen Styra Dr. Sandra González‐Gallardo Dr. Felix Armbruster Dr. Pascual Oña‐Burgos Dipl.‐Chem. Eric Moos Dr. Matthias Vonderach Priv.‐Doz. Dr. Patrick Weis Priv.‐Doz. Dr. Oliver Hampe Dipl.‐Chem. Anneken Grün Dipl.‐Chem. Yvonne Schmitt Prof. Dr. Markus Gerhards Dipl.‐Chem. Fabian Menges Dipl.‐Chem. Maximilian Gaffga Prof. Dr. Gereon Niedner‐Schatteburg Prof. Dr. Frank Breher |
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Affiliation: | 1. Institut für Anorganische Chemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, 76131 Karlsruhe (Germany), Fax: (+49)?721‐608‐470‐21;2. Institut für Physikalische Chemie und Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Postfach 3640, 76021 Karlsruhe (Germany);3. Fachbereich Chemie, Technische Universit?t Kaiserslautern und Landesforschungszentrum OPTIMAS, Erwin‐Schr?dinger‐Strasse, Geb?ude 52, 67663 Kaiserslautern (Germany) |
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Abstract: | A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon‐based metalloligand [κ3N‐Si(3,5‐Me2pz)3Mo(CO)3]? is presented (pz=pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5‐dimethylpyrazolyl)silanide ({Si(3,5‐Me2pz)3}?) with [Mo(CO)3(η6‐toluene)]. The compound features a fac‐coordinated tripodal chelating ligand and an outward pointing, “free” pyramidal silyl donor, which is easily accessible for a secondary coordination to other metal centers. Several bimetallic silyl halido cuprates of the general formula [CuX{μ‐κ1Si:κ3N‐Si(3,5‐Me2pz)3Mo(CO)3}]? (X=Cl, Br, I) have been synthesized. The electronic and structural properties of these complexes were probed in detail by X‐ray diffraction analysis, electrospray mass spectrometry, infrared‐induced multiphoton dissociation studies, cyclic voltammetry, spectroelectrochemistry, gas‐phase photoelectron spectroscopy, as well as UV/Vis and fluorescence spectroscopy. The heterobimetallic complexes contain linear two‐coordinate copper(I) entities with the shortest silicon–copper distances reported so far. Oxidation of the anionic complexes in methylene chloride and acetonitrile solutions at ${E{{0hfill atop 1/2hfill}}}$ =?0.60 and ?0.44 V (vs. ferrocene/ferrocenium (Fc/Fc+)), respectively, shows substantial reversibility. Based on various results obtained from different characterization methods, as well as density functional theory calculations, these oxidation events were attributed to the Mo0/MoI redox couple. |
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Keywords: | bimetallic complexes copper cuprates metalloligands molybdenum |
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