Dinuclear compounds without a metal-metal bond. Dirhodium(III,III)carboxamidates

作者：Angelone, Davide; Draksharapu, Apparao; Browne, Wesley R.^*; Choudhuri, M. M. R.; Crutchley, Robert J.; Xu, Xichen; Xu, Xinfang; Doyle, Michael P.

来源：Inorganica Chimica Acta, 2015, 424: 235-240.

DOI：10.1016/j.ica.2014.09.006

• Rhodium
• Carboxamidate
• Electrochemistry
• Raman spectroscopy

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.

• 出版日期2015-1-1