Electronic Structures, Spectroscopy, and Electrochemistry of [M(diimine)(CN-BR)] (M = Fe, Ru; R = Ph, CF) Complexes.

Complexes with the formula [M(diimine)(CN-BR)], where diimine = bipyridine (bpy), phenanthroline (phen), 3,5-trifluoromethylbipyridine (flpy), R = Ph, CF, and M = Fe, Ru, were synthesized and characterized by X-ray crystal structure analysis, UV-visible spectroscopy, IR spectroscopy, and voltammetry. Three highly soluble complexes, [Fe(bpy)(CN-B(CF))], [Ru(bpy)(CN-B(CF))], and [Ru(flpy)(CN-B(CF))], exhibit electrochemically reversible redox reactions, with large potential differences between the bpy or flpy and M couples of 3.27, 3.52, and 3.19 V, respectively. CASSCF+NEVPT2 calculations accurately reproduce the effects of borane coordination on the electronic structures and spectra of cyanometallates.