An unexpected leading role for [Fe2(CO)6(μ-pdt)] in our understanding of [FeFe]-H2ases and the search for clean hydrogen production

Hogarth, Graeme

doi:10.1016/j.ccr.2023.215174

Cited by 8 publications

(6 citation statements)

References 329 publications

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“…Relatively few examples of di-iron complexes [Fe2(CO)6−xLx(µ-dithiolene)] have been reported [7][8][9][10][11][12]. The hexacarbonyl precursors can be prepared following various pathways, which have been previously reported in the literature [1][2][3][4]11]. The substitution of carbonyl groups by phosphanes, through photochemical, thermal or electrochemical activation, allows us to prepare monosubstituted [Fe2(CO)5L(µ-dithiolene)] and symmetrically disubstituted [Fe2(CO)4L2(µ-dithiolene)] derivatives (one CO being replaced at each iron atom).…”

Section: Resultsmentioning

confidence: 97%

“…Complex 5: IR (CH 2 Cl 2 , cm −1 ): ν(CO), bands overlapped with those of 2. 1 H NMR (CDCl 3 , δ, ppm): 7.68-7.36 (m, 30H, Ph), 3.17 (s, 6H, CH 3 ). 31 P-{ 1 H} NMR (CDCl 3 , δ, ppm) 57.5 (s).…”

Section: Methodsmentioning

confidence: 99%

“…Complex 3: IR (CH 2 Cl 2 , cm −1 ): ν(CO) 2061 (s), 2008 (vs), 1989 (s), 1955 (w), 1717 (w, CO 2 Me). 1 H NMR (CDCl 3 , δ, ppm): 3.80 (d, J = 12.0Hz, 9H, P(OMe) 3 ), 3.66 (s, 6H, CO 2 Me). 31 P-{ 1 H} NMR (CDCl 3 , δ, ppm): 172.1 (s).…”

Section: Methodsmentioning

confidence: 99%

“…Complex 6: IR (CH 2 Cl 2 , cm −1 ):ν(CO) 2036 (s), 1988 (s). 1 H NMR (CDCl 3 , δ, ppm): 3.93 (s, 6H, CO 2 Me), 3.45 (d, J = 12.0Hz, 9H, P(OMe) 3 ). 31 P-{ 1 H} NMR (CDCl 3 , δ, ppm): 168.2 (s).…”

Section: Methodsmentioning

confidence: 99%

“…The chemistry of carbonyl dithiolato di-iron complexes [Fe 2 (CO) 6−x L x (µ-dithiolato)] has attracted a lot of attention during the two last decades in reason of the resemblance of such compounds with the active site of [FeFe]-hydrogenases (H-cluster) (Scheme 1a) and in view to obtain efficient bioinspired non-noble metal electrocatalysts for the reversible H + /H 2 conversion [1][2][3][4][5]. A wide number of di-iron systems with various combinations of thiolate bridges and terminal ligands have been studied in order to tune the electronic and steric properties of the dinuclear site as well as to functionalize the second sphere of coordination with non-innocent functionalities (redox and proton relays) [6].…”

Section: Introductionmentioning

confidence: 99%

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Mono- and Dinuclear Carbonyl Dithiolene Complexes Related to the [FeFe]-Hydrogenases

Kdider,

Elleouet,

Pétillon

et al. 2023

Molbank

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The di-iron carbonyl dithiolene bridged complex [Fe2(CO)6(µ-S2C2(CO2Me)2)] (1) reacts with 1 equivalent of phosphane PR3 (R = Ph, OMe) to give, as major products, monosubstituted derivatives [Fe2(CO)5L(µ-S2C2(CO2Me)2)] (L = PPh3 (2), P(OMe)3 (3)). In the presence of an excess (3–4 equiv.) of P(OMe)3, the cleavage of 1 arises partly and a mixture of the mononuclear species [Fe(CO)(P(OMe)3)2(κ2-S2C2(CO2Me)2)] (4) and 3 is obtained. The compounds 2–4 were analyzed by IR and 1H, 31P-{1H} NMR spectroscopies. Their structures in solid state were determined by X-ray diffraction analyses, which accord with their spectroscopic characteristics.

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Section: Resultsmentioning

confidence: 97%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Mono- and Dinuclear Carbonyl Dithiolene Complexes Related to the [FeFe]-Hydrogenases

Kdider,

Elleouet,

Pétillon

et al. 2023

Molbank

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Modulation of S‐Centered Reactivity: Impact of Terminal Ligands on Alkynyl Addition in [Fe₂(μ‐S₂)(CO)₄L₂] Complexes

Bennour,

Chatelain,

Schollhammer

2024

Eur J Inorg Chem

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The reactivity of complexes [Fe2(µ‐S2)(CO)4L2] (L = CO (1), PPh3 (2)), with lithium alkynylide reagents generated in situ, was investigated. The behavior of the S2‐bridge in these compounds depends on the substitution at the diiron core. The reaction with the hexacarbonyl derivative 1 leads to the formation of the 1,2‐dithiolene bridged complex [Fe2(µ‐SCH=C(R)S)(CO)6] (3R) while the molecule [Fe2(µ‐SH)(µ‐SC≡CR)(CO)4(PPh3)2] (5R), with an open butterfly structure, is isolated when reacting the disubstituted derivative 2. The disubstituted dithiolene complex [Fe2(µ‐SCH=C(Ph)S)(CO)4(PPh3)2] (4Ph) can only be obtained by substitution of carbonyls with PPh3 in 3R. In the presence of piperidine, 5R isomerizes into the 1,1’‐dithiolene bridged derivative 6Ph. The novel compounds 4‐6 were synthesized and characterized by IR and NMR spectroscopies. X‐ray crystallographic studies of the dithiolene complexes 3Ph‐4Ph allowed their structural analysis.

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Improved Access to ‘Butterfly’ Di‐Iron Dithiolates Fe₂(μ‐SR)₂(CO)₆ and their Mono‐ and Bis(phosphine) Adducts

Madlool,

Wingrove,

Paran Rutterford

et al. 2023

ChemistrySelect

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A series of Fe2(μ‐SR)2(CO)6 complexes {R=Me (1Me), Et (1Et), Pr (1Pr), iPr (1iPr), tBu (1tBu), PhCH2 (1Bn) and Ph (1Ph)} have been synthesised. Complexes 1Me, 1tBu, 1Bn and 1Ph were produced by addition of S2R2 to Fe3(CO)12, with all but 1tBu giving excellent yields. Two isomers of 1Me and 1Ph were isolated: the anti‐ and ‘open’ syn‐products. Complexes 1Et, 1Pr and 1iPr were synthesised by treatment of RSH with Fe3(CO)12; two isomers of each complex were isolated. Addition of one equivalent of PR’3 (R’=Me, Cy, Ph) yields the corresponding mono(phosphine) adducts, whilst use of two equivalents of the phosphine (under mild condition, reflux, or irradiation using a deep blue LED depending on SR group) affords the corresponding bis(phosphine) adducts in good to excellent yield. Treatment of 1Ph or 1Me with two equivalents of PMe3 gives the corresponding bis‐substituted phosphines when carried out in the absence of light but leads to oxidative cleavage to Fe(μ‐SPh)2(PMe3)2(CO)2 and Fe(μ‐SMe)2(PMe3)2(CO)2, respectively, under blue light irradiation. Treatment of 1Pr with two equivalents of PCy3 under blue light irradiation leads to reductive breakdown of the Fe−Fe bond to yield Fe(CO)3(PCy3)2, but in the dark at room temperature the desired product Fe2(μ‐SPr)2(PCy3)2(CO)4 may be isolated. Single crystal X‐ray structures were obtained for most family members of ‘butterfly’ {Fe2S2} cores. Cyclic voltammetry shows PMe3‐containing complexes undergo irreversible oxidation, whereas both PCy3 and PPh3 complexes show one (quasi)reversible oxidation, IR of in situ protonation showed COv blue shifting around 80–100 cm−1, while 31P{1H} NMR spectroscopy showed shifting to low field.

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An unexpected leading role for [Fe2(CO)6(μ-pdt)] in our understanding of [FeFe]-H2ases and the search for clean hydrogen production

Cited by 8 publications

References 329 publications

Mono- and Dinuclear Carbonyl Dithiolene Complexes Related to the [FeFe]-Hydrogenases

Mono- and Dinuclear Carbonyl Dithiolene Complexes Related to the [FeFe]-Hydrogenases

Modulation of S‐Centered Reactivity: Impact of Terminal Ligands on Alkynyl Addition in [Fe₂(μ‐S₂)(CO)₄L₂] Complexes

Improved Access to ‘Butterfly’ Di‐Iron Dithiolates Fe₂(μ‐SR)₂(CO)₆ and their Mono‐ and Bis(phosphine) Adducts

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An unexpected leading role for [Fe2(CO)6(μ-pdt)] in our understanding of [FeFe]-H2ases and the search for clean hydrogen production

Cited by 8 publications

References 329 publications

Mono- and Dinuclear Carbonyl Dithiolene Complexes Related to the [FeFe]-Hydrogenases

Mono- and Dinuclear Carbonyl Dithiolene Complexes Related to the [FeFe]-Hydrogenases

Modulation of S‐Centered Reactivity: Impact of Terminal Ligands on Alkynyl Addition in [Fe2(μ‐S2)(CO)4L2] Complexes

Improved Access to ‘Butterfly’ Di‐Iron Dithiolates Fe2(μ‐SR)2(CO)6 and their Mono‐ and Bis(phosphine) Adducts

Contact Info

Product

Resources

About

Modulation of S‐Centered Reactivity: Impact of Terminal Ligands on Alkynyl Addition in [Fe₂(μ‐S₂)(CO)₄L₂] Complexes

Improved Access to ‘Butterfly’ Di‐Iron Dithiolates Fe₂(μ‐SR)₂(CO)₆ and their Mono‐ and Bis(phosphine) Adducts