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Ghosh P, Begum A, Bill E, et al. Molecular and electronic structures of iron(II)/(III) complexes containing N,S-coordinated, closed-shell o-aminothiophenolato(1-) and o-iminothiophenolato(2-) ligands. Inorg Chem. 2003;42(10):3208-15doi: 10.1021/ic020617c.
Ghosh, P., Begum, A., Bill, E., Weyhermüller, T., & Wieghardt, K. (2003). Molecular and electronic structures of iron(II)/(III) complexes containing N,S-coordinated, closed-shell o-aminothiophenolato(1-) and o-iminothiophenolato(2-) ligands. Inorganic chemistry, 42(10), 3208-15. https://doi.org/10.1021/ic020617c
Ghosh, Prasanta, et al. "Molecular and electronic structures of iron(II)/(III) complexes containing N,S-coordinated, closed-shell o-aminothiophenolato(1-) and o-iminothiophenolato(2-) ligands." Inorganic chemistry vol. 42,10 (2003): 3208-15. doi: https://doi.org/10.1021/ic020617c
Ghosh P, Begum A, Bill E, Weyhermüller T, Wieghardt K. Molecular and electronic structures of iron(II)/(III) complexes containing N,S-coordinated, closed-shell o-aminothiophenolato(1-) and o-iminothiophenolato(2-) ligands. Inorg Chem. 2003 May 19;42(10):3208-15. doi: 10.1021/ic020617c. PMID: 12739961.
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Inorg Chem. 2003 May 19;42(10):3208-15. doi: 10.1021/ic020617c.

Molecular and electronic structures of iron(II)/(III) complexes containing N,S-coordinated, closed-shell o-aminothiophenolato(1-) and o-iminothiophenolato(2-) ligands.

Inorganic chemistry

Prasanta Ghosh, Ameerunisha Begum, Eckhard Bill, Thomas Weyhermüller, Karl Wieghardt

Affiliations

  1. Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.

PMID: 12739961 DOI: 10.1021/ic020617c

Abstract

The coordination chemistry of the ligands o-aminothiophenol, H(abt), 4,6-di-tert-butyl-2-aminothiophenol, H[L(AP)], and 1,2-ethanediamine-N,N'-bis(2-benzenethiol), H(4)('N(2)S(2')), with FeCl(2) under strictly anaerobic and increasingly aerobic conditions has been systematically investigated. Using strictly anaerobic conditions, the neutral, air-sensitive, yellow complexes (mu-S,S)[Fe(II)(abt)(2)](2) (1), (mu-S,S)[Fe(II)(L(AP))(2)](2).8CH(3)OH (2), and (mu-S,S)[Fe(II)('H(2)N(2)S(2'))](2).CH(3)CN (3) containing high spin ferrous ions have been isolated where (abt)(1-), (L(AP))(1-), and ('H(2)N(2)S(2'))(2-) represent the respective N,S-coordinated, aromatic o-aminothiophenolate derivative of these ligands. When the described reaction was carried out in the presence of trace amounts of O(2) and [PPh(4)]Br, light-green crystals of [PPh(4)][Fe(II)(abt)(2)(itbs)].[PPh(4)]Br (4) were isolated. The anion [Fe(II)(abt)(2)(itbs)](-) contains a high spin ferrous ion, two N,S-coordinated o-aminophenolate(1-) ligands, and an S-bound, monoanionic o-iminothionebenzosemiquinonate(1-) pi radical, (itbs)(-). Complex 4 possesses an S(t) = 3/2 ground state. In the absence of [PPh(4)]Br and presence of a base NEt(3) and a little O(2), the ferric dimer (mu-NH,NH)[Fe(III)(L(AP))(L(IP))](2) (5a) and its isomer (mu-S,S)[Fe(III)(L(AP))(L(IP))](2) (5b) formed. (L(IP))(2-) represents the aromatic o-iminothiophenolate(2-) dianion of H[L(AP)]. The structures of compounds 2, 4, and 5a have been determined by X-ray crystallography at 100(2) K. Zero-field Mössbauer spectroscopy of 1, 2, 3, and 4 unambiguously shows the presence of high spin ferrous ions: The isomer shift at 80 K is in the narrow range 0.85-0.92 mm s(-1), and a large quadrupole splitting, |DeltaE(Q)|, in the range 3.24-4.10 mm s(-1), is observed. In contrast, 5a and 5b comprise both intermediate spin ferric ions (S(Fe) = 3/2) which couple antiferromagnetically in the dinuclear molecules yielding an S(t) = 0 ground state.

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