Carboxy-functionalized dithiolate di-iron complexes related to the active site of Fe-only hydrogenase

Vijaikanth, Vijendran; Capon, Jean‐François; Gloaguen, Frédéric; Pétillon, François Y.; Schollhammer, Philippe; Talarmin, Jean

doi:10.1016/j.jorganchem.2007.06.042

Cited by 18 publications

(6 citation statements)

References 46 publications

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“…[11] A few carboxy-functionalized diiron mimics have been attached to amine-functionalized surfaces of a solid electrode via amide linkage to prepare an electrocatalytic H 2 -evolving cathode. [45][46][47] Carboxyl has also been known as a useful functional group for covering the surface of nanoparticles. [48][49][50] In this work, two comparable diiron azadithiolate (ADT) complexes C1 and C2 were synthesized as catalysts to construct H 2 evolution hybrid systems.…”

Section: Resultsmentioning

confidence: 99%

Photocatalytic hydrogen evolution by two comparable [FeFe]‐hydrogenase mimics assembled to the surface of ZnS

Song

Wen

Cheng

et al. 2014

Applied Organom Chemis

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Two photocatalytic hydrogen evolution systems were constructed by assembling [FeFe]-hydrogenase mimics, either carboxyl group-containing (C1) or not (C2), on to the surface of ZnS using triethanolamine as electron donor in DMF-H 2 O (9/1, v/v) solution. Upon irradiation for 30 h, the turnover numbers of hydrogen evolution were 3400 and 4950 for the hybrid system C1/ZnS and C2/ZnS, respectively. The photocatalytic activity of the C2/ZnS system was five times higher than the activity of the pristine ZnS, suggesting that the [FeFe]-hydrogenase mimics are crucial toward improving the activity of ZnS. On the basis of the spectroscopic studies and analyses, the photogenerated electron transfer from ZnS to the mimics is probably responsible for the activity enhancement of ZnS. The time dependence of hydrogen generation shows that the mimic C2 is more active than C1. The different hydrogen evolution activity can be attributed to the different adsorption modes of the two [FeFe]-hydrogenase mimics on the surface of ZnS.

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Section: Resultsmentioning

confidence: 99%

Photocatalytic hydrogen evolution by two comparable [FeFe]‐hydrogenase mimics assembled to the surface of ZnS

Song

Wen

Cheng

et al. 2014

Applied Organom Chemis

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“…[Fe 2 (CO) 6 (SCH 2 XCH 2 S)] (X = CH 2 , [15][16][17][18] NR, [19][20][21][22][23][24][25][26][27][28][29][30][31][32] O, [20,33,34] and S; [35] R = alkyl or related species), as hydrogenase mimics that contain dithiolates with three-atom bridges. In addition, complexes with saturated and unsaturated two-atom bridges, such as [Fe 2 (CO) 6 -A C H T U N G T R E N N U N G (SCH 2 CH 2 S)] [18,[36][37][38][39][40][41][42][43] and [Fe 2 (CO) 6 (1,2-S 2 C 6 H 4 )], [44][45][46][47][48][49][50][51] have been synthesized.…”

Section: Introductionmentioning

confidence: 99%

“…Numerous publications12–14 have described the structurally related diiron hexacarbonyl species [Fe 2 (CO) 6 (SCH 2 XCH 2 S)] (X=CH 2 ,15–18 NR,19–32 O,20, 33, 34 and S;35 R=alkyl or related species), as hydrogenase mimics that contain dithiolates with three‐atom bridges. In addition, complexes with saturated and unsaturated two‐atom bridges, such as [Fe 2 (CO) 6 (SCH 2 CH 2 S)]18, 36–43 and [Fe 2 (CO) 6 (1,2‐S 2 C 6 H 4 )],44–51 have been synthesized.…”

Section: Introductionmentioning

confidence: 99%

Diiron Proton Reduction Catalysts Possessing Electron‐Rich and Electron‐Poor Naphthalene‐1,8‐dithiolate Ligands

Wright

Lim

Tilley

2009

Chemistry A European J

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The diiron complexes [Fe(2)(CO)(6)(1,8-S(2)-2,4,5,7-Cl(4)C(10)H(2))] (3), [Fe(2)(CO)(6)(1,8-S(2)C(10)H(6))] (4), and [Fe(2)(CO)(6)(1,8-S(2)-2,7-tBu(2)C(10)H(4))] (5) were synthesized in moderate yield from naphthalene-1,8-dithiols and [Fe(3)(CO)(12)]. They were characterized by IR, (1)H and (13)C NMR spectroscopy and 3 and 4 were characterized by X-ray crystallography. They contain a butterfly Fe(2)S(2) core with Fe-Fe distances of 2.529(1) (3) and 2.506(1) A (4). Cyclic voltammetry (CH(2)Cl(2)/nBu(4)PF(6)) revealed two one-electron reductions, at potentials more positive than those for the related [Fe(2)(CO)(6)(S(CH(2))(3)S)] (1), and one one-electron oxidation. The first reduction of the electron poor 3 (-1.60 V vs Fc/Fc(+)) is 240 mV more positive than the first reduction of the electron rich 5 (-1.84 V). Electrochemical studies revealed that 3-5 facilitate the proton reduction of p-toluenesulfonic acid. The rates of catalysis, with a 95% confidence limit, are 2.4+/-0.8 (1), 5.2+/-0.8 (3), 3.1+/-1.1 (4), 2.9+/-0.6 (5), and 4.5+/-0.2 h(-1) for the related [Fe(2)(CO)(6)(1,2-S(2)C(6)H(4))]. The rates were determined by bulk electrolysis at -1.70 V (Fc/Fc(+)), which correspond to an overpotential of 1.05 V for p-toluenesulfonic acid.

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“…The sum of the bond angles around N1 is 353°, which indicates a degree of planarity, as is typical for N -phenyl derivatives of azadithiolates. [10] The phenyl ring is, however, twisted by 27.2° from the plane defined by the CH 2 –N1–CH 2 group.…”

Section: Resultsmentioning

confidence: 99%

A New Route to Azadithiolato Complexes

et al. 2011

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The reaction of [(MeC5H4)2Ti(SH)2] with cyclic imines with the formula (CH2NR)3 gives 2-aza-1,3-dithiolato chelate complexes [(MeC5H4)2Ti{(SCH2)2NR}] (1, R = Ph; 2, R = Me; 3, R = CH2Ph). These compounds demonstrate that azadithiolate ligands can exist on mononuclear metal centers. The complexes were characterized by 1H NMR spectroscopy, ESI-mass spectrometry, and X-ray crystallography. Variable-temperature 1H NMR studies reveal that the dithiolate ligands undergo ring inversion like other dithiatitanacyclohexanes. Treatment of [(MeC5H4)2Ti{(SCH2)2NPh}] (1) with [Fe(benzylideneacetone)(CO)3] afforded [Fe2{(SCH2)2NPh}(CO)6] in good yield.

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Carboxy-functionalized dithiolate di-iron complexes related to the active site of Fe-only hydrogenase

Cited by 18 publications

References 46 publications

Photocatalytic hydrogen evolution by two comparable [FeFe]‐hydrogenase mimics assembled to the surface of ZnS

Photocatalytic hydrogen evolution by two comparable [FeFe]‐hydrogenase mimics assembled to the surface of ZnS

Diiron Proton Reduction Catalysts Possessing Electron‐Rich and Electron‐Poor Naphthalene‐1,8‐dithiolate Ligands

A New Route to Azadithiolato Complexes

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