Electrocatalytic properties of diiron ethanedithiolate complexes containing benzoate ester

Self Cite

Five monophosphine-substituted diiron propane-1,2-dithiolate complexes as the active site models of [FeFe]-hydrogenases have been synthesized and characterized. Reactions of complex [Fe 2 (CO) 6 {μ-SCH 2 CH(CH 3 )S}] (1) with a monophosphine ligand tris(4-methylphenyl)phosphine, diphenyl-2pyridylphosphine, tris(4-chlorophenyl)phosphine, triphenylphosphine, or tris (4-fluorophenyl)phosphine in the presence of the oxidative agent Me 3 NO·2H 2 O gave the monophosphine-substituted diiron complexes [Fe 2 (CO) 5 (L){μ-SCH 2 CH(CH 3 )S}] [L = P(4-C 6 H 4 CH 3 ) 3 , 2; Ph 2 P(2-C 5 H 4 N), 3; P(4-C 6 H 4 Cl) 3 , 4; PPh 3 , 5; P(4-C 6 H 4 F) 3 , 6] in 81%-94% yields. Complexes 2-6 have been characterized by elemental analysis, spectroscopy, and X-ray crystallography. In addition, electrochemical studies revealed that these complexes can catalyze the reduction of protons to H 2 in the presence of HOAc.

Synthesis, characterization, and electrochemistry of monophosphine‐containing diiron propane‐1,2‐dithiolate complexes related to the active site of [FeFe]‐hydrogenases

Lin

Lǐ

et al. 2019

Self Cite

Selective synthesis of 2‐(5‐oxo‐1‐arylhex‐1‐yn‐3‐yl)phenyl benzoates via FeCl₃‐mediated cascade reactions of propargylamines with β‐enamino ketones

Tang

Zhang

et al. 2020

A mild and efficient FeCl 3-mediated cascade reaction of ortho-hydroxyl propargylamines with β-enamino ketones has been developed. This protocol provided a practical and selective method to synthesize 2-(5-oxo-1-arylhex-1-yn-3-yl)phenyl benzoates via in situ generated alkynyl o-quinone methides following a cascade intermolecular 1,4-conjugate addition/intramolecular nucleophilic addition/reverse Claisen condensation/hydrolysis pathway. Furthermore, a series of 2-(3-oxo-1-arylbutyl)phenyl benzoates with good functional group tolerance were prepared in good to high yields under these reaction conditions.

Diiron ethane‐1,2‐dithiolate complexes with 1,2,3‐thiadiazole moiety: Synthesis, X‐ray crystal structures, electrochemistry and fungicidal activity

Yang

Liu

et al. 2020

Self Cite

Four diiron ethane‐1,2‐dithiolate complexes containing 1,2,3‐thiadiazole moiety have been synthesized and characterized. Esterification of the starting complex [Fe2(CO)6{μ‐SCH2CH(CH2OH)S}] (1) with 4‐methyl‐1,2,3‐thiadiazole‐5‐carboxylic acid in the presence of 4‐dimethylaminopyridine and N,N′‐dicyclohexylcarbodiimide yielded the corresponding ester [Fe2(CO)6{μ‐SCH2CHCH2O2C(4‐C2N2SCH3)S}] (2) in good yield. Further treatment of complex 2 with a phosphine ligand triphenylphosphine, tris(2‐methoxyphenyl)phosphine, or tri(p‐tolyl)phosphine and the decarbonylation reagent Me3NO·2H2O resulted in the formation of phosphine‐substituted analogues [Fe2(CO)5L{μ‐SCH2CHCH2O2C(4‐C2N2SCH3)S}] [L = PPh3, 3; P(2‐C6H4OCH3)3, 4; P(4‐C6H4CH3)3, 5] in 60 − 80% yields. The new complexes 2–5 were characterized by elemental analysis, IR and NMR spectroscopy and further confirmed by X‐ray diffraction analysis. The electrochemical properties were studied by cyclic voltammetry, showing that these complexes can catalyse the reduction of protons to H2 in the presence of HOAc. In addition, the fungicidal activity studies revealed that the hydroxy group possibly play a significant role in the biological activity.