Novel redox active rhodium(III) complex with bis(arylimino)acenaphthene ligand: synthesis, structure and electrochemical studies

摘要

Rhodium trichloride reacts with 1,2-bisR2,6-diisopropylphenyl)iminolacenaphthene (dpp-bian) to afford new octahedral complex mer-Mh(dpp-bian)(H2O)Cl-3]center dot CH2Cl2. The CV of mer-Dth(dpp-bian)(H2O)Cl-3] in MeCN shows an irreversible reduction that corresponds to the Rhill/Rhi couple, followed by reversible or quasi-reversible cathodic waves assigned to reduction of the dpp-bian ligand. DFT calculations confirm the assignment of the redox processes and predict the elimination of two chloride ligands from axial positions upon two-electron reduction of mer-[Rh(dpp-bian)(H20)031 with the formation of a Rht square-planar complex [Rhi(dpp-bian)(H2O)Cl].