The First Binuclear Mn(IV) Complex Containing a Bridging Imidazolate Ligand Exhibits Unique EPR Spectral Features

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The preparation and characterization of the [Mn(III)(dtbsalpn)]2HDCBI precursor will be detailed in a subsequent full paper. [Mn(III)(dtbsalpn)]2HDCBI (1.5 g, 1.2 mmol) was slurried in 120 mL of distilled CH3CN containing 0.10 M tetrabutylammonium hexafluorophosphate and was carefully reacted with 1 equiv of tetrabutylammonium hydroxide under anaerobic conditions. Bulk electrolysis of the solution at 500 mVvsAg wire on a Pt gauze under N2sparging gave a dark green solution after passage of 230 C. The CH3CN solvent was allowed to evaporate, and the green residue was extracted with CH2Cl2. Storage of the solution at −45 °C overnight gave 0.85 g (51% yield) of green microcrystalline [Mn(IV)(dtbsalpn)]2DCBI+PF6-. Anal. Found (calcd): C, 60.5 (60.1); H, 7.1(7.0); N, 5.6 (5.9); Mn, 7.3(7.8). IR:  νCO1710 cm-1, νCN1603 cm-1. Visible:  λmax682 nm, ε = 9500 M-1cm-1. χm= 5.4 μB(298 K). Vapor diffusion of benzene into an acetonitrile solution of [Mn(IV)(dtbsalpn)]2DCBI+PF6-yielded dark-green X-ray quality crystals with three benzene and two acetonitrile molecules of crystallization (Mn2C93F6H121N8O8P, orthorhombic, space groupPbca,a= 21.0211(3),b= 26.8006(2), andc= 32.6466(6) Å, α = β = γ = 90°,V= 18392.4(4) Å3,Z= 8. X-ray diffraction data was collected on a Siemens SMART CCD diffractometer and refined with full-matrix least-squares onF2using 21 826 independent reflections (R= 0.1188, GOF = 1.179).

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