New FeI–FeI Complex Featuring a Rotated Conformation Related to the [2 Fe]H Subsite of [Fe–Fe] Hydrogenase

Munery, Sabrina; Capon, Jean‐François; Gioia, Luca De; Elléouet, Catherine; Greco, Claudio; Pétillon, François Y.; Schollhammer, Philippe; Talarmin, Jean; Zampella, Giuseppe

doi:10.1002/chem.201303316

Cited by 56 publications

(72 citation statements)

References 31 publications

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“…in the butterfly conformation similar to the previously reported models, [41][42][43] and the iron atom is coordinated in a pseudo-square-pyramidal geometry. The substitution of CO by one PPh 3 ligand only has a small effect on the Fe-Fe distance, and the PPh 3 ligand is coordinated to an apical site on Fe(1), and it is positioned roughly trans to the Fe-Fe bond.…”

Section: Wwweurjicorg Full Papersupporting

confidence: 71%

Synthesis and Characterization of Bio‐Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds

et al. 2015

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Three [FeFe]‐hydrogenase model complexes [(μ‐dmedt){Fe(CO)3}2] [1; dmedt = SCH(CH3)CH(CH3)S], [(μ‐dmedt){Fe(CO)3}{Fe (CO)2PPh3}] (1‐PPh3), and [(μ‐dmest){Fe(CO)3}2] [1‐O; dmest = SCH(CH3)CH(CH3)S(O)], 1‐O were synthesized and characterized. These model complexes, which are generally used as the functional biomimics of the hydrogen‐producing dinuclear active site in [FeFe]‐hydrogenase, were used as efficient catalysts for the selective hydroxylation of aromatic compounds to phenols under mild conditions. Because both the dithiolato‐sulfur site and the Fe–Fe bond in the model complexes were possible active oxidation sites, DFT calculations were used to investigate the oxygenated products, that is, the S‐oxygenated products or the Fe‐oxygenated forms of the model complexes, which may be involved in the catalytic cycle. The experimental and computational results indicate that the thermodynamically favored Fe‐oxygenated intermediates dominate the hydroxylation of the aromatic compounds. A possible mechanism for the hydroxylation is also proposed.

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Section: Wwweurjicorg Full Papersupporting

confidence: 71%

Synthesis and Characterization of Bio‐Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds

et al. 2015

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“…In model systems, this geometry can only be reproduced in unsymmetrically substituted complexes, including the Fe(I)Fe-(I) compounds [dppv(OC)Fe(2,2-diethyl-1,3-propanedithiolate)( μ -CO)Fe(CO) 2 ] 266 and [dmpe(OC)Fe-(adt Bn )Fe(CO) 3 ]. 267 …”

Section: [Fefe]-h2asesmentioning

confidence: 99%

Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides

et al. 2016

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Hydrogenase enzymes efficiently process H2 and protons at organometallic FeFe, NiFe, or Fe active sites. Synthetic modeling of the many H2ase states has provided insight into H2ase structure and mechanism, as well as afforded catalysts for the H2 energy vector. Particularly important are hydride-bearing states, with synthetic hydride analogues now known for each hydrogenase class. These hydrides are typically prepared by protonation of low-valent cores. Examples of FeFe and NiFe hydrides derived from H2 have also been prepared. Such chemistry is more developed than mimicry of the redox-inactive monoFe enzyme, although functional models of the latter are now emerging. Advances in physical and theoretical characterization of H2ase enzymes and synthetic models have proven key to the study of hydrides in particular, and will guide modeling efforts toward more robust and active species optimized for practical applications.

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“…142 This and related sterically crowded complexes are of interest as precursors to diiron ditholates that adopt unsymmetrical, “rotated” structures (Figure 8). 140,141,143 …”

Section: Synthesis Of Diiron(i) Dithiolato Carbonyls From Iron(0) mentioning

confidence: 99%

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

2016

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Virtually all organosulfur compounds react with Fe(0) carbonyls to give the title complexes. These reactions are reviewed in light of major advances over the past few decades, spurred by interest in Fe2(μ-SR)2(CO)x centers at the active sites of the [FeFe]-hydrogenase enzymes. The most useful synthetic route to Fe2(μ-SR)2(CO)6 involves the reaction of thiols with Fe2(CO)9 and Fe3(CO)12. Such reactions can proceed via mono-, di-, and triiron intermediates. The reactivity of Fe(0) carbonyls toward thiols is highly chemoselective, and the resulting dithiolato complexes are fairly rugged. Thus, many complexes tolerate further synthetic elaboration directed at the organic substituents. A second major route involves alkylation of Fe2(μ-S2)(CO)6, Fe2(μ-SH)2(CO)6, and Li2Fe2(μ-S)2(CO)6. This approach is especially useful for azadithiolates Fe2[(μ-SCH2)2NR](CO)6. Elaborate complexes arise via addition of the FeSH group to electrophilic alkenes, alkynes, and carbonyls. Although the first example of Fe2(μ-SR)2(CO)6 was prepared from ferrous reagents, ferrous compounds are infrequently used, although the Fe(II)(SR)2 + Fe(0) condensation reaction is promising. Almost invariably low-yielding, the reaction of Fe3(CO)12, S8, and a variety of unsaturated substrates results in C–H activation, affording otherwise inaccessible derivatives. Thiones and related C═S-containing reagents are highly reactive toward Fe(0), often giving complexes derived from substituted methanedithiolates and C–H activation.

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New Fe^I–Fe^I Complex Featuring a Rotated Conformation Related to the [2 Fe]_H Subsite of [Fe–Fe] Hydrogenase

Abstract: Rotated geometry: The first example of a dinuclear iron(I)-iron(I) complex featuring a fully rotated geometry related to the active site of [Fe-Fe] hydrogenase is reported.

Cited by 56 publications

References 31 publications

Synthesis and Characterization of Bio‐Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds

Synthesis and Characterization of Bio‐Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds

Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

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