Iron(III) and iron(II) complexes of 1-thia-4,7-diazacyclononane ([9]aneN2S) and 1,4-dithia-7-azacyclononane ([9]aneNS2). X-Ray structural analyses, magnetic susceptibility, Mössbauer, EPR and electronic spectroscopy

  • Grillo V
  • Gahan L
  • Hanson G
 et al. 
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[Fe([9]aneN2S)2][ClO4]2, [Fe([9]aneN2S)2][ClO4]3 and [Fe([9]aneNS2)2][ClO4]2 ([9]aneN2S = 1-thia-4,7-diazacyclononane and [9]aneNS2 = 1,4-dithia-7-azacyclononane) were prepd. and the latter two characterized by x-ray crystallog. The Mossbauer spectra (isomer shift/mm s-1, quadrupole splitting/mm s-1, 4.2 K) for [Fe([9]aneN2S)2][ClO4]2 (0.52, 0.57), [Fe([9]aneN2S)2][ClO4]3 (0.25, 2.72) and [Fe([9]aneNS2)2][ClO4]2 (0.43, 0.28) are typical for iron(II) and iron(III) complexes. Variable-temp. susceptibility measurements for [Fe([9]aneN2S)2][ClO4]2 (2-300 K) revealed temp.-dependent behavior in both the solid state [2.95 μB (300 K)-0.5 μB (4.2 K)] and soln. (ΔH0 20-22 kJ mol-1, ΔS0 53-60 J mol-1 K-1). For [Fe([9]aneN2S)2][ClO4]3 in the solid state [2.3 μB (300 K)-1.9 μB (4.2 K)] the magnetic data were fit to a simple model (H = -λL·S + μLz) to give the spin-orbit coupling const. (λ) of -260 ± 10 cm-1. The solid-state X-band EPR spectrum of [Fe([9]aneN2S)2][ClO4]3 revealed axial symmetry (g⊥ = 2.607, g‖ = 1.599). Resoln. of g⊥ into two components at Q-band frequencies indicated a rhombic distortion. The low-temp. single-crystal absorption spectra of [Fe([9]aneN2S)2][ClO4]2 and [Fe([9]aneNS2)2][ClO4]2 exhibited addnl. bands which resembled pseudo-tetragonal low-symmetry splitting of the parent octahedral 1A1g → 1T2g and 1A1g → 1T1g transitions. However, the magnitude of these splittings was too large, requiring 10Dq for the thioether donors to be significantly larger than for the amine donors. Instead, these bands were tentatively assigned to weak, low-energy S → FeII charge-transfer transitions. Above 200 K, thermal occupation of the high-spin 5T2g ground state resulted in observation of the 5T2g → 5Eg transition in the crystal spectrum of [Fe([9]aneN2S)2][ClO4]2. From a temp.-dependence study, the sepn. of the low-spin 1A1g and high-spin 5T2g ground states was ∼1700 cm-1. The spectrum of the iron(III) complex [Fe([9]aneN2S)2][ClO4]3 is consistent with a low-spin d5 configuration. [on SciFinder(R)]

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  • Vincent A. Grillo

  • Graeme R. Hanson

  • Robert Stranger

  • Trevor W. Hambley

  • Keith S. Murray

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