Azadithiolates cofactor of the iron-only hydrogenase and its PR3-monosubstituted derivatives: Synthesis, structure, electrochemistry and protonation

Wang, Zhen; Liu, Jianhui; He, Chengjiang; Shi, Jinping; Åkermark, Björn; Sun, Licheng

doi:10.1016/j.jorganchem.2007.08.026

Cited by 55 publications

(43 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…categorized as S, i.e., C.E. > 0.75 (21,51,52,111,126,149,167,182,209). Eight of these show strong catalytic efficiency for a single acid while one, 209, gives C.E.…”

Section: Catalysis Of the Reduction Of Acidsmentioning

confidence: 99%

Review of electrochemical studies of complexes containing the Fe2S2 core characteristic of [FeFe]-hydrogenases including catalysis by these complexes of the reduction of acids to form dihydrogen

Felton

Mebi

Petro

et al. 2009

Journal of Organometallic Chemistry

384

312

View full text Add to dashboard Cite

“…categorized as S, i.e., C.E. > 0.75 (21,51,52,111,126,149,167,182,209). Eight of these show strong catalytic efficiency for a single acid while one, 209, gives C.E.…”

Section: Catalysis Of the Reduction Of Acidsmentioning

confidence: 99%

Review of electrochemical studies of complexes containing the Fe2S2 core characteristic of [FeFe]-hydrogenases including catalysis by these complexes of the reduction of acids to form dihydrogen

Felton

Mebi

Petro

et al. 2009

Journal of Organometallic Chemistry

384

312

View full text Add to dashboard Cite

“…87 When the R substituent is small (R = H, 33 Me, 88 CH 2 CH 2 OH, 89 etc. ), the substituent tends to be axial (i.e., projects nearly parallel with the Fe–Fe bond).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

2016

View full text Add to dashboard Cite

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.

show abstract

“…Based on these significant research findings, the structural and functional models of the Fe-Fe hydrogenases active site have been intensively studied in recent years [6][7][8]. There have been some reports regarding the synthesis and electrochemistry of azadithiolate diiron derivatives (l-SCH 2 ) 2 NR [Fe 2 (CO) 6 ] (R = H, -CH 3 , 4-NO 2 C 6 H 4 , 4-BrC 6 H 4 CH 2 , 2-BrC 6 H 4 , 2-CH 2 C 4 H 3 O) [9][10][11][12][13][14][15][16]. However, the distance between the nitrogen atom in the dithiolated chelate and the iron atom of the active site is comparatively changeless.…”

Section: Introductionmentioning

confidence: 99%

Pendant bases as proton transfer relays in diiron dithiolate complexes inspired by [Fe–Fe] hydrogenase active site

Wang

Jiang

Liu

et al. 2008

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

Azadithiolates cofactor of the iron-only hydrogenase and its PR3-monosubstituted derivatives: Synthesis, structure, electrochemistry and protonation

Cited by 55 publications

References 29 publications

Review of electrochemical studies of complexes containing the Fe2S2 core characteristic of [FeFe]-hydrogenases including catalysis by these complexes of the reduction of acids to form dihydrogen

Review of electrochemical studies of complexes containing the Fe2S2 core characteristic of [FeFe]-hydrogenases including catalysis by these complexes of the reduction of acids to form dihydrogen

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

Pendant bases as proton transfer relays in diiron dithiolate complexes inspired by [Fe–Fe] hydrogenase active site

Contact Info

Product

Resources

About