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Ruthenium complexes of C,C '-bis(ethynyl)carboranes: an investigation of electronic interactions mediated by spherical pseudo-aromatic spacers

Fox, M.A., Roberts, R.L., Baines, T.E., Le Guennic, B., Halet, J.-F., Hartl, F., Yufit, D.S., Albesa- Jové, D., Howard, J.A.K. and Low, P.J. (2008) Ruthenium complexes of C,C '-bis(ethynyl)carboranes: an investigation of electronic interactions mediated by spherical pseudo-aromatic spacers. Journal of the American Chemical Society, 130 (11). pp. 3566-3578. ISSN 0002-7863

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To link to this article DOI: 10.1021/ja0779755

Abstract/Summary

The complexes [Ru(1-C=C-1,10-C2B8H9)(dppe)Cp*] (3a), [Ru(1-C C-1,12-C2B10H11)(dppe)-Cp*] (3b), [{Ru(dppe)Cp*}(2){mu-1,10-(C C)(2)-1,10-C2B8H8}] (4a) and [{Ru(dppe)Cp*}(2){mu-1,12-(C C)2- 1,12-C2B10-H-10}] (4b), which form a representative series of mono- and bimetallic acetylide complexes featuring 10- and 12-vertex carboranes embedded within the dethynyl bridging ligand, have been prepared and structurally characterized. In addition, these compounds have been examined spectroscopically (UV-is-NIR, IR) in all accessible redox states. The significant separation of the two, one-electron anodic waves observed in the cyclic voltammograms of the bimetallic complexes 4a and 4b is largely independent of the nature of the electrolyte and is attributed to stabilization of the intermediate redox products [4a](+) and [4b](+) through interactions between the metal centers across a distance of ca. 12.5 angstrom. The mono-oxidized bimetallic complexes (4a](+) and [4b](+) exhibit spectroscopic properties consistent with a description of these species in terms of valence-localized (class II) mixed-valence compounds, including a unique low-energy electronic absorption band, attributed to an, IVCT-type transition that tails into the IR region. DFT calculations with model systems [4a-H](+) and [4b-H](+) featuring simplified ligand sets reproduce the observed spectroscopic data and localized electronic structures for the mixed-valence cations [4a](+) and [4b](+).

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11252
Uncontrolled Keywords:SIGMA-ACETYLIDE COMPLEXES, NONLINEAR-OPTICAL MATERIALS, TRANSITION-METAL-COMPLEXES, MOLECULAR ELECTRONICS, CHEMICAL-SHIFTS, CHARGE-TRANSFER, ICOSAHEDRAL CARBORANES, DELTA-E-1/2 VALUES, ALKYNYL COMPLEXES, BRIDGING LIGANDS
Publisher:American Chemical Society

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