Class III Delocalization in a Cyanide‐Bridged Trimetallic Mixed‐Valence Complex1. (27th December 2013)

• Record Type: Journal Article
• Authors: Pieslinger, German E.; Alborés, Pablo; Slep, Leonardo D.; Baraldo, Luis M.
• Is Part Of: Angewandte Chemie. Volume 126:Number 5(2014)
• Page Start: 1317
• Page End: 1320
• Publication Date: 2013-12-27
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201307025
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The NIR and IR spectroscopic properties of the cyanide‐bridged complex, <italic>tran</italic>s‐[Ru(dmap)₄{(μ‐CN)Ru(py)₄Cl}₂]³⁺ (py=pyridine, dmap=4‐dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed‐valence species, the first example reported of a cyanide‐bridged system. This has been accomplished by tuning the energy of the fragments in the trimetallic complex to compensate for the intrinsic asymmetry of the cyanide bridge. Moreover, (TD)DFT calculations accurately predict the spectra of the <italic>tran</italic>s‐[Ru(dmap)₄{(μ‐CN)Ru(py)₄Cl}₂]³⁺ ion and confirms its delocalized nature.</p> </abstract>