Abstract
Bis-σ-(phenyl)-tetrakis-μ-(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 Rh26+ 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.
Original language | English (US) |
---|---|
Pages (from-to) | 235-240 |
Number of pages | 6 |
Journal | Inorganica Chimica Acta |
Volume | 424 |
DOIs | |
State | Published - Jan 1 2015 |
Bibliographical note
Publisher Copyright:© 2014 Elsevier B.V. All rights reserved.
Keywords
- Carboxamidate
- Electrochemistry
- Raman spectroscopy
- Rhodium