Electronic structure of linear thiophenolate-bridged heterotrinuclear complexes [LFeMFeL]n(+) (M = Cr, Co, Fe; n = 1-3): Localized vs delocalized models

Glaser T, Beissel T, Bill E, Weyhermuller T, Schunemann V, Meyer-Klaucke W, Trautwein AX, Wieghardt K (1999)
Journal of the American Chemical Society 121(10): 2193-2208.

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Abstract
The reaction of mononuclear [LFeIII] where L represents the trianionic ligand 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane with CrSO4. 5H2O, CoCl2. 6H2O, or Fe(BF4)2. 6H2O and subsequent oxidation with ferrocenium hexafluorophosphate or NO(BF4) or reduction with [(tmcn)Mo(CO)3] (tmcn = 1,4,7-trimethyl-1,4,7-triazacyclononane) produced an isostructural series of [LFeMFeL]n+ complexes, the following salts of which were isolated as crystalline solids: (i) [LFeCrFeL](PF6)n with n = 1 (1a), n = 2 (1b), and n = 3 (1c); (ii) [LFeCoFeL]Xn with X = BPh4 and n = 2 (2b) and X = PF6 and n = 3 (2c); (iii) [LFeFeFeL](BPh4)n with n = 2 (3b) and n = 3 (3c). All compounds contain Linear trinuclear cations (face-sharing octahedral) with an N3Fe(mu-SR)3M(mu-SR)3FeN3 core structure. The electron structure of all complexes has been studied by Fe and M K-edge X-ray absorption near edge structure (XANES), UV-vis, and EPR spectroscopy, variable-temperature, variable-field susceptibility measurements, and Mossbauer spectroscopy (in zero and applied field). The following electronic structures have been established: (1a) FeII(ls)CrIIIFeII(ls) (ls = low-spin) with a spin ground state of St = 3/2; (1c) FeIII(ls)CrIIIFeIII(ls) with an St = 1/2 ground state; (2c) FeIII(ls)CoIII(ls)FeIII(ls) with an St = 1 ground state; (3c) FeIII(ls)FeIII(ls)FeIII(ls) with an St = 1/2 ground state. For 1b (St = 2) it is found that the two iron ions are spectroscopically equivalent (Fe2.5) and, therefore, the excess electron is delocalized (class III): [LFe2.5CrIIIFe2.5L]2+. For 2b clearly two different iron sites prevail at low temperatures (4.2 K); at higher temperatures (>200 K) they become equivalent on the Mossbauer time scale. Thus, 2b is class II with temperature-dependent electron hopping between the FeII and FeIII ions. 3b is again fully delocalized (class III) with an St = 1 ground state; the excess electron is delocalized over all three iron sites. The electronic structure of all complexes is discussed in terms of double exchange and superexchange mechanisms.
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Glaser T, Beissel T, Bill E, et al. Electronic structure of linear thiophenolate-bridged heterotrinuclear complexes [LFeMFeL]n(+) (M = Cr, Co, Fe; n = 1-3): Localized vs delocalized models. Journal of the American Chemical Society. 1999;121(10):2193-2208.
Glaser, T., Beissel, T., Bill, E., Weyhermuller, T., Schunemann, V., Meyer-Klaucke, W., Trautwein, A. X., et al. (1999). Electronic structure of linear thiophenolate-bridged heterotrinuclear complexes [LFeMFeL]n(+) (M = Cr, Co, Fe; n = 1-3): Localized vs delocalized models. Journal of the American Chemical Society, 121(10), 2193-2208.
Glaser, T., Beissel, T., Bill, E., Weyhermuller, T., Schunemann, V., Meyer-Klaucke, W., Trautwein, A. X., and Wieghardt, K. (1999). Electronic structure of linear thiophenolate-bridged heterotrinuclear complexes [LFeMFeL]n(+) (M = Cr, Co, Fe; n = 1-3): Localized vs delocalized models. Journal of the American Chemical Society 121, 2193-2208.
Glaser, T., et al., 1999. Electronic structure of linear thiophenolate-bridged heterotrinuclear complexes [LFeMFeL]n(+) (M = Cr, Co, Fe; n = 1-3): Localized vs delocalized models. Journal of the American Chemical Society, 121(10), p 2193-2208.
T. Glaser, et al., “Electronic structure of linear thiophenolate-bridged heterotrinuclear complexes [LFeMFeL]n(+) (M = Cr, Co, Fe; n = 1-3): Localized vs delocalized models”, Journal of the American Chemical Society, vol. 121, 1999, pp. 2193-2208.
Glaser, T., Beissel, T., Bill, E., Weyhermuller, T., Schunemann, V., Meyer-Klaucke, W., Trautwein, A.X., Wieghardt, K.: Electronic structure of linear thiophenolate-bridged heterotrinuclear complexes [LFeMFeL]n(+) (M = Cr, Co, Fe; n = 1-3): Localized vs delocalized models. Journal of the American Chemical Society. 121, 2193-2208 (1999).
Glaser, Thorsten, Beissel, T, Bill, E, Weyhermuller, T, Schunemann, V, Meyer-Klaucke, W, Trautwein, AX, and Wieghardt, K. “Electronic structure of linear thiophenolate-bridged heterotrinuclear complexes [LFeMFeL]n(+) (M = Cr, Co, Fe; n = 1-3): Localized vs delocalized models”. Journal of the American Chemical Society 121.10 (1999): 2193-2208.
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