Syntheses and Structures of Three Complexes of Formulas [L<sub>3</sub>Co(μ<sub>2</sub>-O<sub>2</sub>P(Bn)<sub>2</sub>)<sub>3</sub>CoL′][L″], Featuring Octahedral and Tetrahedral Cobalt(II) Geometries; Variable-Temperature Magnetic Susceptibility Measurement and Analysis on [(py)<sub>3</sub>Co(μ<sub>2</sub>-O<sub>2</sub>PBn<sub>2</sub>)<sub>3</sub>Co(py)][ClO<sub>4</sub>]
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The syntheses and structural properties of three dinuclear complexes [L3Co(μ2-O2P(Bn)2)3CoL′][L″] [one ionic L3 = py3, L′ = py, L″ = ClO4– (1) and two molecular L3 = py3, L′ = Cl (2) and L3 = py, μ2-NO3–, L′ = py (3)] are reported. Complexes feature octahedral CoII sites bridged by three dibenzylphosphinate ligands to a tetrahedrally ligated CoII site, with the remaining coordination sites occupied by py, nitrato, and Cl ligands. The Co–Co distances are 4.248 Å at 291 K and 4.265 Å at 100 K for 1 and 4.278 and 4.0313(7) Å for 2 and 3, respectively at 100 K. A fit of the low-temperature magnetic susceptibility data was derived for complex 1 with g = 2.25, TIP = 700 × 10–6 cm3 mol –1, λ = −173 cm–1, κ = 0.93, ν = −3.9, Δ = 630 cm–1, J = 0.15 cm–1, and θ = −1.8 resulting in R(χM) = 2.5 × 10–5 and R(χMT) = 5.8 × 10–5.
