Kinetics of the Reactions between [(RS)2Fe(µ-S)2M(µ-S)2Fe(SR)2]n− (M = Mo, R = Ph, n = 2; M = V, R = Et, n = 3) and [Fe(SR)4]2−: Key Steps in the Assembly of Cuboidal Fe—S-based Clusters

Cui, Zhen; Henderson, Richard A.

doi:10.1007/s11243-006-0020-6

Cited by 3 publications

(1 citation statement)

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“…The reaction of [S 2 Mo(m-S) 2 Fe(SPh) 2 ] 2À with [Fe(SPh) 4 ] 2À produces the dicuboidal cluster [{MoFe 3 S 4 (SPh) 3 } 2 (m-SPh) 3 ] 3À in a three stage process studied by 1 H-NMR spectroscopy and stopped-flow spectrophotometry. 92 A kinetic study on the catalytic dihydrogen reduction of a series of substrates by the Chini-cluster, [Pt 12 (CO) 24 ] 2À , indicates two catalytic pathways with an observed rate constant, k obs = (k 1 [S] + k 2 ); where k 1 refers to complex formation between the cluster and the electron-acceptor substrate, followed by electron transfer; the second pathway (k 2 ) involves formation of the solvated cluster (independent of [S]), followed by electron transfer. 93 Fragmentation of the hydroxo-chalcogenide cluster [W 3 Se 4 (OH) 3 (dmpe) 3 ] + in acetic acid has been studied by stopped-flow, ESI-MS and 31 P NMR.…”

Section: Clustersmentioning

confidence: 99%

Reaction mechanisms in solution

Haines

2007

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Section: Clustersmentioning

confidence: 99%

Reaction mechanisms in solution

Haines

2007

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Iron–Amide–Sulfide and Iron–Imide–Sulfide Clusters: Heteroligated Core Environments Relevant to the Nitrogenase FeMo Cofactor

et al. 2012

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Heteroligated cluster cores consisting of weak-field iron, strongly basic nitrogen anions, and sulfide are of interest with respect to observed and conjectured environments in the FeMo cofactor of nitrogenase. Selective syntheses have been developed to achieve such environments with tert-butyl-substituted amide and imide core ligands. A number of different routes were employed, including nominal ligand substitution and oxidative addition reactions, as well as novel transformations involving the combination of different cluster precursors. New cluster products include precursor Fe(2)(μ-NH(t)Bu)(2)[N(SiMe(3))(2)](2) (6), Fe(2)(μ-NH(t)Bu)(2)(μ-S)[N(SiMe(3))(2)](2) (7), which has a rare confacial bitetrahedral geometry previously unknown in iron chemistry, [Fe(2)(μ-N(t)Bu)(μ-S)Cl(4)](2-) (2), and cuboidal [Fe(4)(μ(3)-N(t)Bu)(3)(μ(3)-S)Cl(4)](-) (8), [Fe(4)(μ(3)-N(t)Bu)(2)(μ(3)-S)(2)Cl(4)](2-) (9), and [Fe(4)(μ(3)-N(t)Bu)(μ(3)-S)(3)Cl(4)](2-) (10), as well as selenide-substituted derivatives Fe(2)(μ-NH(t)Bu)(2)(μ-Se)[N(SiMe(3))(2)](2) (7-Se) and [Fe(4)(μ(3)-N(t)Bu)(μ(3)-Se)(3)Cl(4)](2-) (10-Se). The imide-sulfide clusters complete the compositional sets [Fe(2)(μ-N(t)Bu)(n)(μ-S)(2-n)Cl(4)](2-) (n = 0-2) and [Fe(4)(μ(3)-N(t)Bu)(n)(μ(3)-S)(4-n)Cl(4)](z) (n = 0-4), represented previously only by the all-imide and all-sulfide core congeners, and they share chemical and physical properties with the parent homoleptic core species. All imide-sulfide cores are compositionally stable and show no evidence of core ligand exchange over days in solution. Beyond structural differences, the impact of mixed core ligation is most evident in redox potentials, which show progressive decreases of -435 (for z = 1-/2-) or -385 mV (for z = 2-/3-) for each replacement of sulfide by the more potent imide donor, and a corresponding effect may be expected for the interstitial heteroligand in the FeMo cofactor. Cluster 10 presents an [Fe(4)NS(3)] core framework virtually isometric with the isostructural [Fe(4)S(3)X] subunit of the FeMo cofactor, thus providing a synthetic structural representation for this portion of the cofactor core.

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Rates of protonation of thiolate and sulfide ligands in mononuclear complexes and Fe-S-based clusters: implications for metalloenzymes

Henderson¹

2012

BioInorganic Reaction Mechanisms

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Kinetics of the Reactions between [(RS)2Fe(µ-S)2M(µ-S)2Fe(SR)2]n− (M = Mo, R = Ph, n = 2; M = V, R = Et, n = 3) and [Fe(SR)4]2−: Key Steps in the Assembly of Cuboidal Fe—S-based Clusters

Cited by 3 publications

References 28 publications

Reaction mechanisms in solution

Reaction mechanisms in solution

Iron–Amide–Sulfide and Iron–Imide–Sulfide Clusters: Heteroligated Core Environments Relevant to the Nitrogenase FeMo Cofactor

Rates of protonation of thiolate and sulfide ligands in mononuclear complexes and Fe-S-based clusters: implications for metalloenzymes

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