Boronated Cyanometallates

Thirteen boronated cyanometallates [M(CN-BR₃)₆]^3/4/5– [M = Cr, Mn, Fe, Ru, Os; BR₃ = BPh₃, B(2,4,6,-F₃C₆H₂)₃, B(C₆F₅)₃] and one metalloboratonitrile [Cr(NC-BPh₃)₆]^3– have been characterized by X-ray crystallography and spectroscopy [UV–vis–near-IR, NMR, IR, spectroelectrochemistry, and magnetic circular dichroism (MCD)]; CASSCF+NEVPT2 methods were employed in calculations of electronic structures. For (t_2g)⁵ electronic configurations, the lowest-energy ligand-to-metal charge-transfer (LMCT) absorptions and MCD <i>C</i>-terms in the spectra of boronated species have been assigned to transitions from cyanide π + B–C borane σ orbitals. CASSCF+NEVPT2 calculations including t_1u and t_2u orbitals reproduced t_1u/t_2u → t_2g excitation energies. Many [M(CN-BR₃)₆]^3/4– complexes exhibited highly electrochemically reversible redox couples. Notably, the reduction formal potentials of all five [M(CN-B(C₆F₅)₃)₆]^3– anions scale with the LMCT energies, and Mn(I) and Cr(II) compounds, [K(18-crown-6)]₅[Mn(CN-B(C₆F₅)₃)₆] and [K(18-crown-6)]₄[Cr(CN-B(C₆F₅)₃)₆], are surprisingly stable. Continuous-wave and pulsed electron paramagnetic resonance (EPR; hyperfine sublevel correlation) spectra were collected for all Cr(III) complexes; as expected, ¹⁴N hyperfine splittings are greater for (Ph₄As)₃[Cr(NC-BPh₃)₆] than for (Ph₄As)₃[Cr(CN-BPh₃)₆].