1. Heterobimetallic Cuprates Consisting of a Redox-Switchable, Silicon-Based Metalloligand: Synthesis, Structures, and Electronic Properties.
- Author
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Styra, Steffen, González‐Gallardo, Sandra, Armbruster, Felix, Oña‐Burgos, Pascual, Moos, Eric, Vonderach, Matthias, Weis, Patrick, Hampe, Oliver, Grün, Anneken, Schmitt, Yvonne, Gerhards, Markus, Menges, Fabian, Gaffga, Maximilian, Niedner‐Schatteburg, Gereon, and Breher, Frank
- Subjects
CUPRATES ,BIMETALLIC catalysts ,SILICON ,BIOMASS energy ,CHEMICAL synthesis - Abstract
A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon-based metalloligand [κ
3 N-Si(3,5-Me2 pz)3 Mo(CO)3 ]− is presented (pz=pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5-dimethylpyrazolyl)silanide ({Si(3,5-Me2 pz)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-κ1 Si:κ3 N-Si(3,5-Me2 pz)3 Mo(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 ${E{{0\hfill \atop 1/2\hfill}}}$=−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. [ABSTRACT FROM AUTHOR]- Published
- 2013
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