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Heterobimetallic Cuprates Consisting of a Redox-Switchable, Silicon-Based Metalloligand: Synthesis, Structures, and Electronic Properties
Ist Teil von
Chemistry : a European journal, 2013-06, Vol.19 (26), p.8436-8446
Ort / Verlag
Weinheim: WILEY-VCH Verlag
Erscheinungsjahr
2013
Link zum Volltext
Quelle
Wiley Online Library
Beschreibungen/Notizen
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 ${E{{0\hfill \atop 1/2\hfill}}}$=−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.
Putting metals together: The preparation, structures, and electronic properties of bimetallic silyl halido cuprates consisting of an anionic silicon‐based metalloligand are reported, together with detailed studies on their gas‐phase properties and their fluorescence and redox behavior in solution (see figure).