Sensitivity of a Strained C–C Single Bond to Charge Transfer: Redox Activity in Mononuclear and Dinuclear Ruthenium Complexes of Bis(arylimino)acenaphthene (BIAN) Ligands

The new compounds [Ru­(acac)₂(BIAN)], BIAN = bis­(arylimino)­acenaphthene (aryl = Ph (<b>1a</b>), 4-MeC₆H₄ (<b>2a</b>), 4-OMeC₆H₄ (<b>3a</b>), 4-ClC₆H₄ (<b>4a</b>), 4-NO₂C₆H₄ (<b>5a</b>)), were synthesized and structurally, electrochemically, spectroscopically, and computationally characterized. The α-diimine sections of the compounds exhibit intrachelate ring bond lengths 1.304 Å < d­(CN) < 1.334 and 1.425 Å < d­(CC) < 1.449 Å, which indicate considerable metal-to-ligand charge transfer in the ground state, approaching a Ru^III(BIAN^•–) oxidation state formulation. The particular structural sensitivity of the strained peri-connecting C–C bond in the BIAN ligands toward metal-to-ligand charge transfer is discussed. Oxidation of [Ru­(acac)₂(BIAN)] produces electron paramagnetic resonance (EPR) and UV–vis–NIR (NIR = near infrared) spectroelectrochemically detectable Ru^III species, while the reduction yields predominantly BIAN-based spin, in agreement with density functional theory (DFT) spin-density calculations. Variation of the substituents from CH₃ to NO₂ has little effect on the spin distribution but affects the absorption spectra. The dinuclear compounds {(μ-tppz)­[Ru­(Cl)­(BIAN)]₂}­(ClO₄)₂, tppz = 2,3,5,6-tetrakis­(2-pyridyl)­pyrazine; aryl (BIAN) = Ph ([<b>1b</b>]­(ClO₄)₂), 4-MeC₆H₄ ([<b>2b</b>]­(ClO₄)₂), 4-OMeC₆H₄ ([<b>3b</b>]­(ClO₄)₂), 4-ClC₆H₄ ([<b>4b</b>]­(ClO₄)₂), were also obtained and investigated. The structure determination of [<b>2b</b>]­(ClO₄)₂ and [<b>3b</b>]­(ClO₄)₂ reveals <i>trans</i> configuration of the chloride ligands and unreduced BIAN ligands. The DFT and spectroelectrochemical results (UV–vis–NIR, EPR) indicate oxidation to a weakly coupled Ru^IIIRu^II mixed-valent species but reduction to a tppz-centered radical state. The effect of the π electron-accepting BIAN ancillary ligands is to diminish the metal–metal interaction due to competition with the acceptor bridge tppz