Syntheses and structures of three complexes of formulas [L3Co(μ2 -O2P(Bn)2)3 CoL′][L″], featuring octahedral and tetrahedral cobalt(II) geometries; Variable-temperature magnetic susceptibility measurement and analysis on [(py)3 Co(μ2 -O2 PBn2 )3 Co(py)][ClO4]

Document Type

Article

Publication Date

5-7-2012

Department

Department of Chemistry

Abstract

The syntheses and structural properties of three dinuclear complexes [L 3Co(μ 2-O 2P(Bn) 2) 3CoL′][L″] [one ionic L 3 = py 3, L′ = py, L″ = ClO 4- (1) and two molecular L 3 = py 3, L′ = Cl (2) and L 3 = py, μ 2-NO 3-, L′ = py (3)] are reported. Complexes feature octahedral Co II sites bridged by three dibenzylphosphinate ligands to a tetrahedrally ligated Co II 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 cm 3 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(π M) = 2.5 × 10 -5 and R(π MT) = 5.8 × 10 -5.

Publication Title

Inorganic Chemistry

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