Reactions of Monoanions [(μ-RE)(μ-E)Fe2(CO)6]− and Dianions [(μ-E)2Fe2(CO)6]2− (E = Se, S) with N-Substituted Benzimidoyl Chlorides, Leading to Novel Butterfly Fe/E Cluster Complexes

Song, Li‐Cheng; Mei, Shiyue; Feng, Cui-Ping; Gong, Feng-Hua; Ge, Jin; Hu, Qing‐Mei

doi:10.1021/om1002655

Cited by 16 publications

(4 citation statements)

References 56 publications

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“…The second step involves the intramolecular nucleophilic attack of N atoms in M 1 (due to the fact that N -arylmethyl substituents in D–F are stronger electron-donating groups than the N - p -methoxyphenyl substituent in C ) at one of their two Fe atoms with cleavage of one Se–Fe bond to give the seven-membered metallacycle (2Fe2Se1N2C)-containing intermediates M 2 . Actually, this step is very similar to the previously reported intramolecular nucleophilic attack at iron followed by loss of the Fe-bound ligand that occurred in some butterfly Fe/S cluster complexes. , The third step involves extrusion of one Se atom from the seven-membered metallacycle in M 2 to give the more stable six-membered metallacycle (2Fe1Se1N2C)-containing butterfly [2Fe1Se1N1C] complexes 7–9 . The third step is actually similar to the previously reported extrusion of Se from the p -MeC 6 H 4 SO 2 Se-bridged butterfly Fe/E complexes (μ-RE)(μ- p -MeC 6 H 4 SO 2 Se)Fe 2 (CO) 6 (E = S or Se) .…”

Section: Resultssupporting

confidence: 82%

Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H₂ Evolution Catalyzed by [(μ-SeCH₂)(μ-CH₂NCH₂Ph)]Fe₂(CO)₆

et al. 2019

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As models of [FeFe]-H2 ases, 13 butterfly Fe/E (E = S, Se, or Te) complexes (1–13) have been prepared by various synthetic methods. Treatment of [(μ-SCH2)2CH2]Fe2(CO)6 (A) and [(μ-SCH2)2CHO2CPh]Fe2(CO)6 (B) with the in situ-generated N-heterocyclic carbenes (NHC) IMe/Mes, IVinyl/Mes, IMes, and IMe gave the corresponding carbene-substituted butterfly [2Fe2S] complexes [(μ-SCH2)2CH2]Fe2(CO)5(IMe/Mes) (1), [(μ-SCH2)2CH2]Fe2(CO)5(IVinyl/Mes) (2), [(μ-SCH2)2CHO2CPh]Fe2(CO)5(IMes) (3), and [(μ-SCH2)2CHO2CPh]Fe2(CO)4(IMe)2 (4), respectively. Although the N-p-methoxyphenyl-substituted 1,2,4-diselenazolidine C reacted with Fe3(CO)12 to give the expected butterfly [2Fe2Se] complex [(μ-SeCH2)2NC6H4OMe-p]Fe2(CO)6 (5) and further reaction of 5 with PPh3 afforded its PPh3-substituted derivative [(μ-SeCH2)2NC6H4OMe-p]Fe2(CO)5(PPh3) (6), the N-arylmethyl-substituted 1,2,4-diselenazolidines D–F reacted with Fe3(CO)12 to give the first butterfly [2Fe1Se1N1C] complexes [(μ-SeCH2)(μ-CH2NR)]Fe2(CO)6 (7, R = PhCH2; 8, R = NC5H4CH2-p; 9, R = CpFeC5H4CH2), unexpectedly. More interestingly, on the basis of synthesizing the first ODTe-bridged butterfly [2Fe2Te] complex [(μ-TeCH2)2O]Fe2(CO)6 (10), the NHC-substituted butterfly [2Fe2Te] complexes [(μ-TeCH2)2O]Fe2(CO)5(L) (11, L = IMe/Mes; 12, L = IMes; 13, L = IMe) were prepared by reactions of complex 10 with the corresponding NHC ligands. In addition, while all of the new complexes 1–13 were structurally characterized, complex 7 was found to be a H2-producing catalyst from benzoic acid and p-toluenesulfonic acid under cyclic voltammetry conditions.

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Section: Resultssupporting

confidence: 82%

Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H₂ Evolution Catalyzed by [(μ-SeCH₂)(μ-CH₂NCH₂Ph)]Fe₂(CO)₆

et al. 2019

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“…341 Related reactions with the imidoyl chloride PhC-(Cl)═NPh give Fe 2 ( μ -SC(Ph)═NPh) 2 (CO) 6 and Fe 2 ( μ -SC(Ph)═NPh)( μ -SR)(CO) 6 . 342 Diacid chlorides ( o -phthaloyl, succinoyl, glutaryl) react with Li 2 Fe 2 ( μ -S) 2 (CO) 6 to give the dithioesters (Scheme 34). 341 Treatment of LiFe 2 ( μ -SR)( μ -S)(CO) 6 with diacid halides gives thermally labile derivatives in which two Fe 2 units are linked.…”

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

confidence: 99%

“…Thioester-bridged diiron hexacarbonyls are readily prepared by acylation of Li 2 Fe 2 (μ-S) 2 (CO) 6 and Fe 2 (μ-SR)(μ-SCOR′)(CO) 6 . Related reactions with the imidoyl chloride PhC(Cl)NPh give Fe 2 (μ-SC(Ph)NPh) 2 (CO) 6 and Fe 2 (μ-SC(Ph)NPh)(μ-SR)(CO) 6 . Diacid chlorides ( o -phthaloyl, succinoyl, glutaryl) react with Li 2 Fe 2 (μ-S) 2 (CO) 6 to give the dithioesters (Scheme ).…”

Section: Synthesis Of Diiron(i) Dithiolato Carbonyls From Iron(i) Pre...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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“…Over the past few decades, several diiron dithiolato complexes that mimic the butterfly [Fe 2 S 2 ] subcluster of the H-cluster have been synthesized by altering the bridge in [Fe 2 (CO) 6 {μ-S(bridge)S}] (Figure b) and tested as electrocatalysts. − Moreover, these complexes have been modified to contain heavier chalcogen atoms such as selenium or tellurium instead of sulfur . In addition, substitution of the CO ligands in [Fe 2 (CO) 6 {μ-S(CH 2 YCH 2 )S}] (Y = CH 2 , NR, O, SiR 2 , PhPO) by cyanide, phosphanes, ,, phosphites, ,,− carbenes, ,,, nitrosyl, or sulfides , to produce mono-, di-, tri-, and tetrasubstituted complexes has been extensively studied. ,− Furthermore, other efforts have focused on synthesizing macrocyclic complexes that contain two [Fe 2 S 2 ] clusters connected by different linkers, which provide two catalytic active centers.…”

Section: Introductionmentioning

confidence: 99%

[FeFe]-Hydrogenase H-Cluster Mimics with Various −S(CH₂)_nS– Linker Lengths (n = 2–8): A Systematic Study

et al. 2017

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The effect of the nature of the dithiolato ligand on the physical and electrochemical properties of synthetic H-cluster mimics of the [FeFe]-hydrogenase is still of significant concern. In this report we describe the cyclization of various alkanedithiols to afford cyclic disulfide, tetrasulfide, and hexasulfide compounds. The latter compounds were used as proligands for the synthesis of a series of [FeFe]-hydrogenase H-cluster mimics having the general formulas [Fe(CO){μ-S(CH)S}] (n = 4-8), [Fe(CO){μ-S(CH)S}] (n = 6-8), and [Fe(CO){(μ-S(CH)S)}] (n = 6-8). The resulting complexes were characterized by H andC{H} NMR and IR spectroscopic techniques, mass spectrometry, and elemental analysis as well as X-ray analysis. The purpose of this research was to study the influence of the systematic increase of n from 2 to 7 on the redox potentials of the models and the catalytic ability in the presence of acetic acid (AcOH) by applying cyclic voltammetry.

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Reactions of Monoanions [(μ-RE)(μ-E)Fe₂(CO)₆]⁻ and Dianions [(μ-E)₂Fe₂(CO)₆]²⁻ (E = Se, S) with N-Substituted Benzimidoyl Chlorides, Leading to Novel Butterfly Fe/E Cluster Complexes

Cited by 16 publications

References 56 publications

Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H₂ Evolution Catalyzed by [(μ-SeCH₂)(μ-CH₂NCH₂Ph)]Fe₂(CO)₆

Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H₂ Evolution Catalyzed by [(μ-SeCH₂)(μ-CH₂NCH₂Ph)]Fe₂(CO)₆

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

[FeFe]-Hydrogenase H-Cluster Mimics with Various −S(CH₂)_nS– Linker Lengths (n = 2–8): A Systematic Study

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Reactions of Monoanions [(μ-RE)(μ-E)Fe2(CO)6]− and Dianions [(μ-E)2Fe2(CO)6]2− (E = Se, S) with N-Substituted Benzimidoyl Chlorides, Leading to Novel Butterfly Fe/E Cluster Complexes

Cited by 16 publications

References 56 publications

Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H2 Evolution Catalyzed by [(μ-SeCH2)(μ-CH2NCH2Ph)]Fe2(CO)6

Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H2 Evolution Catalyzed by [(μ-SeCH2)(μ-CH2NCH2Ph)]Fe2(CO)6

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

[FeFe]-Hydrogenase H-Cluster Mimics with Various −S(CH2)nS– Linker Lengths (n = 2–8): A Systematic Study

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Reactions of Monoanions [(μ-RE)(μ-E)Fe₂(CO)₆]⁻ and Dianions [(μ-E)₂Fe₂(CO)₆]²⁻ (E = Se, S) with N-Substituted Benzimidoyl Chlorides, Leading to Novel Butterfly Fe/E Cluster Complexes

Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H₂ Evolution Catalyzed by [(μ-SeCH₂)(μ-CH₂NCH₂Ph)]Fe₂(CO)₆

Synthetic and Structural Studies of [FeFe]-Hydrogenase Models Containing a Butterfly Fe/E (E = S, Se, or Te) Cluster Core. Electrocatalytic H₂ Evolution Catalyzed by [(μ-SeCH₂)(μ-CH₂NCH₂Ph)]Fe₂(CO)₆

[FeFe]-Hydrogenase H-Cluster Mimics with Various −S(CH₂)_nS– Linker Lengths (n = 2–8): A Systematic Study