Dinuclear compounds without a metal-metal bond. Dirhodium(III,III)carboxamidates
| Autor: | Robert J. Crutchley, Wesley R. Browne, Mohommad M. R. Choudhuri, Michael P. Doyle, Apparao Draksharapu, Davide Angelone, Xinfang Xu, Xichen Xu |
|---|---|
| Přispěvatelé: | Synthetic Organic Chemistry |
| Jazyk: | angličtina |
| Rok vydání: | 2015 |
| Předmět: |
Resonance Raman spectroscopy
chemistry.chemical_element Photochemistry Electrochemistry Copper Rhodium Inorganic Chemistry PADDLEWHEEL COMPLEX ATOMS symbols.namesake Crystallography Carboxamidate chemistry Raman spectroscopy Materials Chemistry symbols Physical and Theoretical Chemistry Cyclic voltammetry Conformational isomerism Isomerization SET |
| Zdroj: | Inorganica chimica acta-Articles, 424, 235-240. ELSEVIER SCIENCE SA LAUSANNE |
| ISSN: | 0020-1693 |
| DOI: | 10.1016/j.ica.2014.09.006 |
| Popis: | Bis-sigma-(phenyl)-tetrakis-mu-(capralactamato)dirhodium(III), formed by oxidative reactions of dirhodium(II) carboxamidates with arylboronic acids promoted by copper(II), exists in two non-interconvertable conformations. In these conformational isomers the caprolactamate ligands are oriented around dirhodium( III) as a propeller with apparent C4 symmetry and in a biplanar array. Cyclic voltammetry and spectroelectrochemistry as well as Raman and resonance Raman spectroscopy of the conformationally distinct Rh-2(6+) carboxamidates have been obtained in order to explore the origin of their non-interconversion. Differences in their vibrational spectra occur only in the low wavenumber spectral region, but there is a 250 mV difference in oxidation potential between conformational isomers consistent with a substantial difference ground state energies. Notably, spectroelectrochemical data show that oxidation does not result in isomerization. (C) 2014 Elsevier B.V. All rights reserved. |
| Databáze: | OpenAIRE |
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