[Fe6Se9(SR)2]4- Clusters (R = Me, CH2Ph): Synthesis and Characterization, and the X-Ray Structure of (PhCH2NEt3)4[Fe6Se9(SMe)2]

Strasdeit, Henry; Krebs, Bernt; Henkel, Gerald

doi:10.1515/znb-1987-0509

Cited by 21 publications

(5 citation statements)

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“…Selected metrical features are summarized in Table ; there is no systematic trend in these bond lengths and angles with oxidation state. The [M 2 Fe 4 (μ 2 -Q) 6 (μ 3 -Q) 2 (μ 4 -Q)] connectivity pattern was first and most frequently demonstrated with [Fe 6 S 9 (SR) 2 ] 4– , − and it is also found in the selenide clusters [Fe 6 Se 9 (SR) 2 ] 4– . , The only other heterometal clusters of this type are [(edt) 2 Mo 2 Fe 6 S 9 ] 3–/4– whose cores are isoelectronic with 12 and 13 but differ by the presence of trigonal-bipyramidal molybdenum sites . The isomer shift of the 4– cluster was interpreted in terms of the charge distribution (Mo 4+ 2 Fe 3+ 2 Fe 2+ 2 ), corresponding to that of 13 .…”

Section: Resultsmentioning

confidence: 99%

“…The [M 2 Fe 4 (μ 2 -Q) 6 (μ 3 -Q) 2 (μ 4 -Q)] connectivity pattern was first and most frequently demonstrated with [Fe 6 S 9 (SR) 2 ] 4− , 44−48 and it is also found in the selenide clusters [Fe 6 Se 9 (SR) 2 ] 4− . 49,50 The only other heterometal clusters of this type are [(edt) 2 Mo 2 Fe 6 S 9 ] 3−/4− whose cores are isoelectronic with 12 and 13 but differ by the presence of trigonal-bipyramidal molybdenum sites. 52 The isomer shift of the 4− cluster was interpreted in terms of the charge distribution (Mo 4+ 2 Fe 3+ 2 Fe 2+ 2 ), corresponding to that of 13.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Selenium as a Structural Surrogate of Sulfur: Template-Assisted Assembly of Five Types of Tungsten–Iron–Sulfur/Selenium Clusters and the Structural Fate of Chalcogenide Reactants

et al. 2012

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Syntheses of five types of tungsten-iron-sulfur/selenium clusters–incomplete cubanes, single cubanes, edge-bridged double cubanes (EBDCs), PN-type clusters, and double-cuboidal clusters–have been devised based on the concept of template-assisted assembly. The template reactant is six-coordinate [(Tp*)WVIS3]1−, which in the assembly systems organizes FeII,III and sulfide/selenide into cuboidal [(Tp*)WFe2S3] or cubane [(Tp*)WFe3S3Q] units. With appropriate terminal iron ligation, these units are capable of independent existence or may be transformed into higher nuclearity species. Selenide is used as a surrogate for sulfide in cluster assembly in order to determine by X-ray structures the position occupied by an external chalcogenide nucleophile or an internal chalcogenide atom in product clusters. Specific incorporation of selenide is demonstrated by formation of [WFe3S3Se]2+,3+ cubane cores. Reductive dimerization of the cubane leads to the EBDC core [W2Fe6S6Se2]2+ containing μ4-Se sites. Reaction of these species with HSe− affords the PN-type cores [W2Fe6S6Se3]1+ in which selenide occupies μ6-Se and μ2-Se sites. Reaction of [(Tp*)WS3]1−, FeCl2, and Na2Se results in the double cuboidal [W2Fe4S6Se3]2+,0 core with μ2-Se and μ4-Se bridges. It is highly probable that in analogous sulfide-only assembly systems, external and internal sulfide reactants occupy corresponding positions in cluster products. The results further demonstrate the viability of template-assisted cluster synthesis inasmuch as the reduced (Tp*)WS3 unit is present in all clusters. Structures, zero-field Mössbauer data, and redox potentials are presented for all cluster types. (Tp* = tris(pyrazolyl)hydroborate(1−))

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Selenium as a Structural Surrogate of Sulfur: Template-Assisted Assembly of Five Types of Tungsten–Iron–Sulfur/Selenium Clusters and the Structural Fate of Chalcogenide Reactants

et al. 2012

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“…To investigate the locus of the attacking nucleophile in the product core, we have utilized hydroselenide as a surrogate reactant for hydrosulfide. Sets of weak-field sulfide/selenide clusters with corresponding compositions and the same or very similar terminal ligands are known and include those with rhomboidal Fe 2 Q 2 , , cuboidal and linear Fe 3 Q 4 , , cubane-type Fe 4 Q 4 , − Fe 6 Q 9 , ,, and heterometal cubane-type MFe 3 S 4 (M = Mo, , Ni) cores. In these clusters, selenide substitution of sulfide conserves structures and induces several property differences, among them red-shifted LMCT transitions, small positive displacements of redox potentials, and increases in Fe−(μ 2 - 4 -Q) bond distances.…”

Section: Resultsmentioning

confidence: 99%

Edge-Bridged Mo₂Fe₆S₈ to P^N-Type Mo₂Fe₆S₉ Cluster Conversion: Structural Fate of the Attacking Sulfide/Selenide Nucleophile

Berlinguette

Holm

2006

J. Am. Chem. Soc.

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Reaction of the edge-bridged double cubane cluster [(Tp)(2)M(2)Fe(6)S(8)(PEt(3))(4)] (1; Tp = hydrotris(pyrazolyl)borate(1-)) with hydrosulfide affords the clusters [(Tp)(2)M(2)Fe(6)S(9)(SH)(2)](3)(-)(,4)(-) (M = Mo (2), V), which have been established as the first structural (topological) analogues of the P(N) cluster of nitrogenase. The synthetic reaction is an example of core conversion, resulting in the transformation M(2)Fe(6)(mu(3)-S)(6)(mu(4)-S)(2) (C(i)) --> M(2)Fe(6)(mu(2)-S)(2)(mu(3)-S)(6)(mu(6)-S) (C(2)(v)), the reaction pathway of which is unknown. The most prominent structural feature of P(N)-type clusters is the mu(6)-S atom, which bridges six iron atoms in two MFe(3)S(3) cuboidal halves of the cluster. The initial issue in core conversion is the origin of the mu(6)-S atom. Utilizing SeH(-) as a surrogate reactant for SH(-) in the system 1/SeH(-)/L(-) in acetonitrile, a series of selenide clusters [(Tp)(2)Mo(2)Fe(6)S(8)SeL(2)](3)(-) (L(-) = SH(-) (4), SeH(-) (5), EtS(-) (6), CN(-) (7)) was prepared. The electrospray mass spectra of 4 and 6 revealed inclusion of one Se atom in each cluster, and (1)H NMR spectra and crystallographic refinements of 4-7 indicated that this atom was disordered over the two mu(2)-S/Se positions. The clusters {[(Tp)(2)Mo(2)Fe(6)S(9)](mu(2)-S)}(2)(5)(-) (8) and {[(Tp)(2)Mo(2)Fe(6)S(8)Se](mu(2)-Se)}(2)(5)(-) (9) were prepared from 2 and 5, respectively, and shown to be isostructural. They consist of two P(N)-type cluster units bridged by two mu(2)-S or mu(2)-Se atoms. It is concluded that, in the preparation of 2, the probable structural fate of the attacking nucleophile is as a mu(2)-S atom, and that the mu(3)-S and mu(6)-S atoms of the product cluster derive from precursor cluster 1. Cluster fragmentation during P(N)-type cluster synthesis is unlikely.

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“…Br(2)-Fe(l)-P(2) 107. 7 (1) and Hg(PEt3)2Cl241 (105.5°). For these phosphine complexes, there is a tendency for the X-M-X angle to decrease as the Shannon tetrahedral radius42 of the metal ion increases, suggesting a progressive alleviation of ligand-ligand repulsion as bond lengths increase.…”

Section: Resultsmentioning

confidence: 99%

Hexanuclear iron-sulfur basket clusters: topological isomers of prismanes. Synthesis, structure, and reactions

Synder¹,

Holm²

1988

Inorg. Chem.

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Thus neither e" nor ew for CN" can be even approximated from this treatment. It is also unrealistic to accept the best-fit f values, even when the propagated error turns out to be small, because changes in f induce smaller changes in the transition energies than would such factors as the inclusion of additional K+ (or [Cr-(CN)6]3~) ions in the model.The value of the Trees parameter, 211 cm™1 using the Pean structure, appears large by comparison with the 70-cm™1 value for the free Cr3+ ion.8 Smaller values of the Trees parameter place the 2T2g levels too high in energy when B and C are chosen to fit the quartets and the 2Eg and 2Tlg levels.The fit to the experimental energies is definitely better for the Pean geometry, but the model includes too many approximations to justify a prediction that this is the structure at 13 K, the temperature at which the excitation spectrum was measured. With either the Pean or P\ geometry, including a cation field of reasonable magnitude yields a better fit to experiment than no field at all. It is not obvious that this should be so, because at zero cation field the calculated 2T2g splitting is too large, while the 2Eg (20) Flint, C.

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[Fe₆Se₉(SR)₂]^4- Clusters (R = Me, CH₂Ph): Synthesis and Characterization, and the X-Ray Structure of (PhCH₂NEt₃)₄[Fe₆Se₉(SMe)₂]

Abstract: (1)The compounds (PhCH2NEt3)4[Fe6Se9(SMe)2] and (Et4N)4[Fe6Se9(SCH2Ph)2] (2) have been isolated in good yields from Fe(SR)3 (R = Me, CH2Ph)/“Na2… Show more

Cited by 21 publications

References 17 publications

Selenium as a Structural Surrogate of Sulfur: Template-Assisted Assembly of Five Types of Tungsten–Iron–Sulfur/Selenium Clusters and the Structural Fate of Chalcogenide Reactants

Selenium as a Structural Surrogate of Sulfur: Template-Assisted Assembly of Five Types of Tungsten–Iron–Sulfur/Selenium Clusters and the Structural Fate of Chalcogenide Reactants

Edge-Bridged Mo₂Fe₆S₈ to P^N-Type Mo₂Fe₆S₉ Cluster Conversion: Structural Fate of the Attacking Sulfide/Selenide Nucleophile

Hexanuclear iron-sulfur basket clusters: topological isomers of prismanes. Synthesis, structure, and reactions

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[Fe6Se9(SR)2]4- Clusters (R = Me, CH2Ph): Synthesis and Characterization, and the X-Ray Structure of (PhCH2NEt3)4[Fe6Se9(SMe)2]

Abstract: (1)The compounds (PhCH2NEt3)4[Fe6Se9(SMe)2] and (Et4N)4[Fe6Se9(SCH2Ph)2] (2) have been isolated in good yields from Fe(SR)3 (R = Me, CH2Ph)/“Na2… Show more

Cited by 21 publications

References 17 publications

Selenium as a Structural Surrogate of Sulfur: Template-Assisted Assembly of Five Types of Tungsten–Iron–Sulfur/Selenium Clusters and the Structural Fate of Chalcogenide Reactants

Selenium as a Structural Surrogate of Sulfur: Template-Assisted Assembly of Five Types of Tungsten–Iron–Sulfur/Selenium Clusters and the Structural Fate of Chalcogenide Reactants

Edge-Bridged Mo2Fe6S8 to PN-Type Mo2Fe6S9 Cluster Conversion: Structural Fate of the Attacking Sulfide/Selenide Nucleophile

Hexanuclear iron-sulfur basket clusters: topological isomers of prismanes. Synthesis, structure, and reactions

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[Fe₆Se₉(SR)₂]^4- Clusters (R = Me, CH₂Ph): Synthesis and Characterization, and the X-Ray Structure of (PhCH₂NEt₃)₄[Fe₆Se₉(SMe)₂]

Edge-Bridged Mo₂Fe₆S₈ to P^N-Type Mo₂Fe₆S₉ Cluster Conversion: Structural Fate of the Attacking Sulfide/Selenide Nucleophile