Sn(III) and Ge(III) in the thiophenolato-bridged complexes [LFeSnFeL](n+) and [LFeGeFeL](n+) (n=2, 3; L=1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane)

Glaser T, Bill E, Weyhermuller T, Meyer-Klaucke W, Wieghardt K (1999)
Inorganic Chemistry 38(11): 2632-2642.

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The reaction of mononuclear [LFe(III)] where L represents the trianionic ligand 1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane with Pb(ClO(4))(2). 3H(2)O in methanol affords the heterotrinuclear complex [LFePbFeL](ClO(4))(2) (1). Similarly, with SnSO(4) or GeI(2) as starting material in an acetonitrile/water mixture and CH(2)Cl(2), respectively, the reaction with [LFe(III)] yields crystalline materials of [LFeSnFeL](PF(6))(2) (2a) and [LFeGeFeL](PF(6))(2) (3a) upon addition of NaPF(6). Complexes 2a and 3a can be one-electron oxidized by [Ni(III)(tacn)(2)](ClO(4))(3) (tacn = 1,4,7-triazacyclononane) to give [LFeSnFeL](ClO(4))(3) (2b) and [LFeGeFeL](ClO(4))(3) (3b). The crystal structures of [LFeSnFeL](BPh(4))(2). 6CH(3)CN (2a*), [LFeSnFeL](ClO(4))(3). 4.5(CH(3))(2)CO (2b*), and [LFeGeFeL](BPh(4))(2). 6CH(3)CN (3a*) have been determined by single-crystal X-ray crystallography. The trinuclear cations consist of three face-sharing octahedra connected by six thiolato bridges affording the core N(3)Fe(mu-S)(3)M(mu-S)(3)FeN(3) (M = Sn,Ge). Fe and Sn(Ge) K edge X-ray absorption spectroscopy on 2a, 2b, and 3a, 3b established that the one-electron oxidations affect exclusively the iron ions whereas the oxidation state of the central Sn(Ge) remains unaffected. (119)Sn((57)Fe) Mossbauer spectroscopy, magnetochemistry, and EPR spectroscopy prove that both the Sn and Ge ions in the di- and trications are trivalent since the unpaired electron in 2b and 3b displays substantial 5s and 4s character, respectively. In contrast, in 1, an oxidation state distribution of l.s.Fe(III)Pb(II)l.s.Fe(III) prevails. Complexes 1, 2a, and 3a possess a diamagnetic ground state whereas 2b and 3b have an S(t) = 1/2 ground state.
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Glaser T, Bill E, Weyhermuller T, Meyer-Klaucke W, Wieghardt K. Sn(III) and Ge(III) in the thiophenolato-bridged complexes [LFeSnFeL](n+) and [LFeGeFeL](n+) (n=2, 3; L=1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry. 1999;38(11):2632-2642.
Glaser, T., Bill, E., Weyhermuller, T., Meyer-Klaucke, W., & Wieghardt, K. (1999). Sn(III) and Ge(III) in the thiophenolato-bridged complexes [LFeSnFeL](n+) and [LFeGeFeL](n+) (n=2, 3; L=1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry, 38(11), 2632-2642.
Glaser, T., Bill, E., Weyhermuller, T., Meyer-Klaucke, W., and Wieghardt, K. (1999). Sn(III) and Ge(III) in the thiophenolato-bridged complexes [LFeSnFeL](n+) and [LFeGeFeL](n+) (n=2, 3; L=1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry 38, 2632-2642.
Glaser, T., et al., 1999. Sn(III) and Ge(III) in the thiophenolato-bridged complexes [LFeSnFeL](n+) and [LFeGeFeL](n+) (n=2, 3; L=1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry, 38(11), p 2632-2642.
T. Glaser, et al., “Sn(III) and Ge(III) in the thiophenolato-bridged complexes [LFeSnFeL](n+) and [LFeGeFeL](n+) (n=2, 3; L=1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane)”, Inorganic Chemistry, vol. 38, 1999, pp. 2632-2642.
Glaser, T., Bill, E., Weyhermuller, T., Meyer-Klaucke, W., Wieghardt, K.: Sn(III) and Ge(III) in the thiophenolato-bridged complexes [LFeSnFeL](n+) and [LFeGeFeL](n+) (n=2, 3; L=1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane). Inorganic Chemistry. 38, 2632-2642 (1999).
Glaser, Thorsten, Bill, E, Weyhermuller, T, Meyer-Klaucke, W, and Wieghardt, K. “Sn(III) and Ge(III) in the thiophenolato-bridged complexes [LFeSnFeL](n+) and [LFeGeFeL](n+) (n=2, 3; L=1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane)”. Inorganic Chemistry 38.11 (1999): 2632-2642.
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