Crystal Structure of a Dinuclear Co Complex with Doubly Bridged Fluoride and Peroxo Ligands: μ-fluoro μ-peroxo bis{tris(2-pyridylmethyl)amine} dicobalt(III) tris(tetrafluoroborate), [Co₂(μ-F)(μ-O₂)(tpa)₂](BF₄)₃

Abstract

The reaction of a methanol solution containing Co(BF₄)₂·6H₂O and tris(2-pyridylmethyl)amine (tpa) afforded the unexpected dinuclear cobalt(III)-peroxo complex [Co₂(μ-F)(μ-O₂)(tpa)₂](BF₄)₃, where the two metal centers are simultaneously doubly bridged by one fluoride ion such that BF₄^- is a fluoride source. It crystallizes in the triclinic space group P1 with a = 10.452(3)Å, b = 12.529(3)Å, c = 16.708(5)Å, α = 106.410(4)°, β = 106.916(4)°, γ = 90.2807(13)°, V = 1999.0(9)ų, D_calc = 1.678 g/cm³, and Z = 2. The R1 [I > 2σ(I)] and wR2 (all data) values are 0.0450 and 0.1679, respectively, for all 9093 independent reflections.