Trichloro(1,4,7-trithiacyclononane-S,S',S'')iron(III), [FeCl3(C6H12S3)]

Ballester, Jorge; Parker, O. J.; Breneman, G. L.

doi:10.1107/s0108270193012247

Cited by 6 publications

(3 citation statements)

References 5 publications

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“…46 Instead, the unique iron atom would appear to be biased toward the high-spin Fe(III) condition based on the mean Fe-S bond distance of 2.57(3) Å in high-spin [Fe([9]aneS 3 )Cl 3 ]. 47 The difference between mean values of the core Fe(1)-Se and Fe(2-4)-Se bond lengths (0.18 Å) is consistent with the difference between high-spin octahedral and tetrahedral Fe(III) radii (0.15 Å). 48 Whatever may be the exact charge distribution, the magnetic coupling within the [Fe 4 Se 4 ] 2+ core is not strongly perturbed compared to other clusters.…”

Section: Examination Of the Isotropic Shift Data Insupporting

confidence: 68%

Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe₄Q₄]²⁺Clusters (Q = S, Se)

Zhou

Holm

1997

Inorg. Chem.

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The [1:3] site-differentiated cubane-type clusters [Fe4Q4(LS3)Cl]2- (Q = S, Se; LS3 = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzenate(3−)) undergo substitution reactions at the unique iron site with a variety of ligands including thiolates, phenolates, cyclic triamines and a trisulfide, imidazoles, and tertiary phosphines. Reactions are readily followed because of the extreme sensitivity of isotropically shifted resonances to the nature of ligand L‘ in the product clusters [Fe4Q4(LS3)L‘]2-,-. Isotropic shifts and redox potentials are reported for over 40 clusters, including many cluster pairs differing only in the core chalcogenide atom. In this way, comparative properties of sulfide and selenide clusters can be elicited. It is shown that the larger isotropic shifts consistently observed for selenide clusters and dominantly contact in nature arise from larger magnetic susceptibilities, which indicate a lesser extent of antiferromagnetic coupling. It is further demonstrated that, without exception, redox potentials of selenide clusters are more positive than those of sulfide clusters, usually by 20−60 mV, at parity of ligation. The difference in potentials of ca. 300 mV between the [Fe4S4]2+,+ couples of [Fe4S4(LS3)(SEt)]2- and [Fe4S4(LS3)(Im)]- (Im = imidazole) clusters is the best available estimate of the intrinsic potential difference between protein-bound [Fe4S4(Cys-S)4] and [Fe4S4(Cys-S)3(His-N)] clusters. The ligand LS3 undergoes spontaneous transfer between [Fe4S4]2+, [Fe4Se4]2+, and [MoFe3S4]3+ cores in reactions whose equilibrium constants are near the statistical value. The ligand binding affinity order PhS- > PhO- > CN- ≫ Cl- for [Fe4Q4]2+ cores was established. When taken together with earlier results from this laboratory, a comprehensive picture of ligand binding to single iron sites in [Fe4Q4]2+ clusters emerges.

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Section: Examination Of the Isotropic Shift Data Insupporting

confidence: 68%

Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe₄Q₄]²⁺Clusters (Q = S, Se)

Zhou

Holm

1997

Inorg. Chem.

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“…The average Fe−S bond distances confirm this assignment. Published Fe−S bond distances for octahedrally coordinated iron ions with at least three sulfur ligands are found in the range 2.26−2.34 Å for ls Fe II , − 2.23−2.36 Å for ls Fe III , ,− 2.51−2.57 Å for hs Fe II , ,,,− and 2.57 Å for hs Fe III 3 Selected Average Bond Distances (Å) and Angles (deg) of the Trication [LFeCrFeL] 3+ in Crystals of 1c *, of the Trication [LFeCoFeL] 3+ in 2c , and of the Dication [LFeFeFeL] 2+ in 3b * Determined by X-ray Crystallography 1c * 2c 3b * Fe t −N 2.055(10) 2.038(3) 2.059(8) Fe t −S 2.257(3) 2.234(1) 2.236(3) M c −S 2.398(3) 2.286(1) 2.297(2) Fe t ···M c 2.941(3) 2.870(1) 2.848(2) Fe t −S−M c 78.30(10) 78.82(4) 77.81(8) …”

Section: Resultsmentioning

confidence: 99%

“…2.23-2.36 Å for ls Fe III ,46,[53][54][55][56][57][58] 2.51-2.57 Å for hs Fe II ,39,41,53,[59][60][61][62][63][64] and 2.57 Å for hs Fe III 65. …”

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confidence: 99%

Electronic Structure of Linear Thiophenolate-Bridged Heterotrinuclear Complexes [LFeMFeL]ⁿ⁺ (M = Cr, Co, Fe; n = 1−3): Localized vs Delocalized Models

et al. 1999

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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]X n 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(μ-SR)3M(μ-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 Mössbauer 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 S t = 3/2; (1c) FeIII(ls)CrIIIFeIII(ls) with an S t = 1/2 ground state; (2c) FeIII(ls)CoIII(ls)FeIII(ls) with an S t = 1 ground state; (3c) FeIII(ls)FeIII(ls)FeIII(ls) with an S t = 1/2 ground state. For 1b (S t = 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 Mössbauer 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 S t = 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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Conformational analysis of 9-crown-3, 9-thiacrown-3 and 9-azacrown-3

Al-Jallal

El-Azhary

2017

Journal of Molecular Graphics and Modelling

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Trichloro(1,4,7-trithiacyclononane-S,S',S'')iron(III), [FeCl3(C6H12S3)]

Cited by 6 publications

References 5 publications

Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe₄Q₄]²⁺Clusters (Q = S, Se)

Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe₄Q₄]²⁺Clusters (Q = S, Se)

Electronic Structure of Linear Thiophenolate-Bridged Heterotrinuclear Complexes [LFeMFeL]ⁿ⁺ (M = Cr, Co, Fe; n = 1−3): Localized vs Delocalized Models

Conformational analysis of 9-crown-3, 9-thiacrown-3 and 9-azacrown-3

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Trichloro(1,4,7-trithiacyclononane-S,S',S'')iron(III), [FeCl3(C6H12S3)]

Cited by 6 publications

References 5 publications

Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe4Q4]2+Clusters (Q = S, Se)

Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe4Q4]2+Clusters (Q = S, Se)

Electronic Structure of Linear Thiophenolate-Bridged Heterotrinuclear Complexes [LFeMFeL]n+ (M = Cr, Co, Fe; n = 1−3): Localized vs Delocalized Models

Conformational analysis of 9-crown-3, 9-thiacrown-3 and 9-azacrown-3

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Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe₄Q₄]²⁺Clusters (Q = S, Se)

Comparative Isotropic Shifts, Redox Potentials, and Ligand Binding Propensities of [1:3] Site-Differentiated Cubane-Type [Fe₄Q₄]²⁺Clusters (Q = S, Se)

Electronic Structure of Linear Thiophenolate-Bridged Heterotrinuclear Complexes [LFeMFeL]ⁿ⁺ (M = Cr, Co, Fe; n = 1−3): Localized vs Delocalized Models