Electronic structure of paramagnetic clusters of transition metal ions. 3. Magnetic properties and scattered wave description of the electronic structure of the hexanuclear octahedral cluster [Fe6(μ3−S)8(PEt3)6] (BPh4)2

Spin-polarized Xα–SW calculations of [Fe₆(μ₃?S)₈(PH₃)₆]²⁺ as a model of the cluster [Fe₆(μ₃?S)₈(PEt₃)₆] (BPh₄)₂ have been performed. The highest occupied energy levels are well separated from empty levels, and up to a maximum of eight electrons can be unpaired, giving a maximum spin state with S = 4. This electronic state is consistent with the magnetic data of [Fe₆(μ₃?S)₈(PEt₃)₆](BPh ₄)₂, which have been interpreted using the Heisenberg–Dirac–Van Vleck exchange spin Hamiltonian. The S = 4 state arises from the magnetic coupling between five low-spin (S_i = 1/2) and one intermediate-spin (S = 3/2) iron(III) center. © 1994 John Wiley & Sons, Inc.