| Abstrakt: |
Compounds (C)[Mn(1,2-pdt)], where C = PhAs ( 1a) or EtN ( 1b), (EtN)[Fe(1,2-pdt)] ( 2) and (PhP)[Ni(1,2-pdt)]·2MeCN ( 3), where 1,2-pdt = propane-1,2-dithiolate, were prepared by reaction of disodium 1,2-propanedithiolate with metal chlorides. Compound ( 1a) crystallizes in the orthorhombic space group P with a = 10.854(2), b = 22.562(4), c = 24.545(6) Å, V = 6010.8 Å, Z = 4. The structure was solved from 3003 reflections with I≥3σ(I) and refined to R(Rw) = 0.038(0.045). The two identical fragments [Mn(1,2-pdt)] dimerize by bridging through sulfur atoms, on from each of the monomers, to form a rectangular Mn(μ-S) unit. Compound ( 3) crystallizes in the monoclinic space group P2/c with a = 10.802(2), b = 30.111(7), c = 9.907(3) Å, β = 93.60(3)°, V = 3216.0 Å, Z = 2. The structure was refined to R(Rw) = 0.063(0.068) from 2256 reflection with I≥3σ(I). The anion of ( 3) is formed by chelation of two [Ni(1,2-pdt)] units to a central Ni atom. The three NiS planes form a chair with a crystallographic centre of symmetry. Complexes ( 1) and ( 2) are paramagnetic and dissociate into monomers in solution while ( 3) is diamagnetic and may not dissociate. Solid state magnetic susceptibility measurements showed the ground state spins of the Mn and Fe ions in ( 1) and ( 2) to be S = 2 and S = 3/2, respectively, and the two metal atoms in both molecules exhibit antiferromagnetic interactions. The unsymmetrical 1,2-pdt ligand chelates to the metal such that the methyl substituent on the terminal carbon atom is remote from the bridging sulfur. [ABSTRACT FROM AUTHOR] |
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