The study of unusual Rh(II) complexes is becoming a new trend in current rhodium chemistry research. However, most of rhodium(II) complexes exist as a diamagnetic dimer with Rh-Rh bond. The current report demonstrates that adjusting the steric bulkiness of ligand can produce the paramagnetic rhodium(II) dimer without Rh-Rh bond, that is, unsaturated (BDI)Rh(COE) react with I<sub>2</sub> to generate a paramagnetic β-diiminate rhodium(II) halide-bridged dimers, which was confirmed by single-crystal X-ray diffraction (see figure) and NMR. The solution NMR and the DC magnetic susceptibility measurement both confirmed it is paramagnetic. DFT calculation showed that the oxidation mainly occurred at the rhodium center and the Rh(II) complex might be formed from the reaction between rhodium(III) intermediate with Rh(0) reactant.

New paramagnetic rhodium(II) dimers without Rh-Rh bonds

251st National Meeting (2016)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.