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In this report, two diiron ethane-1,2-dithiolate carbonyl complexes with bridging 1,3-bis(diphenylphosphino)propane (dppp) or tris(3-fluorophenyl)phosphine have been synthesized and characterized. Treatment of complex [Fe2(CO)6(µ-SCH2CH2S)] (1) with a diphosphine ligand dppp or a monophosphine ligand tris(3-fluorophenyl)phosphine using Me3NO·2H2O as the decarbonylating reagent afforded the corresponding derivatives [{Fe2(CO)5(µ-SCH2CH2S)}2(Ph2PCH2CH2CH2PPh2)] (2) and [Fe2(CO)5(µ-SCH2CH2S){P(3-C6H4F)3}] (3) in 82% and 92% yields, respectively. Complexes 2 and 3 have been characterized by elemental analysis, IR, NMR spectroscopy, as well as confirmed by single crystal X-ray diffraction analysis. Moreover, the electrochemistry of these complexes were studied by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

Two diiron ethane-1,2-dithiolate complexes were prepared and structurally characterized. Reactions of the parent complex [Fe2(CO)6(μ-SCH2CH2S)] (1) with tris(4-trifluoromethylphenyl)phosphine or triethyl phosphite and Me3NO·2H2O as the oxidative reagent resulted in the formation of the phosphine-substituted analog [Fe2(CO)5{P(4-C6H4CF3)3}(μ-SCH2CH2S)] (2) and phosphite-substituted analogue [Fe2(CO)5{P(OCH2CH3)3}(μ-SCH2CH2S)] (3) in 84% and 78% yields, respectively. The new complexes 2 and 3 were characterized by elemental analysis, IR, NMR spectroscopy, and single crystal X-ray diffraction analysis. Moreover, the electrochemical properties of both complexes were studied by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

Two diiron toluene-3,4-dithiolate complexes with a phosphine ligand or a phosphite ligand were prepared and characterized. Treatment of complex [Fe2(CO)6{µ-SC6H3(CH3)S}] (1) with one equivalent of ethyldiphenylphosphine or methyldiphenylphosphinite and the decarbonylation agent Me3NO·2H2O gave analogues [Fe2(CO)5(Ph2PCH2CH3){µ-SC6H3(CH3)S}] (2) [Fe2(CO)5(Ph2POCH3){µ-SC6H3(CH3)S}] (3) and in 84% and 61% yields, respectively. Both analogues have been characterized by spectroscopy, elemental analysis, and X-ray crystallography. The electrochemical properties were probed by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

We report a novel diiron propane-1,3-dithiolate complex [Fe2(CO)5PH(C10H15)2(μ-SCH2CH2CH2S)] containing a di-1-adamantylphosphine ligand. Trimethylamine N-oxide-induced decarbonylation of complex [Fe2(CO)6(μ-SCH2CH2CH2S)] followed by reaction with di-1-adamantylphosphine yielded the target product in 86% yield. The title compound was identified by spectroscopy, elemental analysis, as well as further determined by single crystal X-ray diffraction analysis. Electrochemical properties were studied by cyclic voltammetry without or with HOAc. Interestingly, the fungicidal activity of the title compound showed moderate activity against Phytophthora infestans, Pyricularia oryae, Botrytis cinerea, and Physalospora piricola. [ABSTRACT FROM AUTHOR]

In this report, we describe the preparation of two diiron butane-1,2-dithiolate pentacarbonyl complexes with tris(3-fluorophenyl)phosphine or tris(3-chlorophenyl)phosphine as mimics for the active site of [FeFe]-hydrogenases. The two complexes were synthesized by the reactions of hexacarbonyl complex [Fe2(CO)6{µ-SCH2CH(CH2CH3)S}] (1) with the corresponding tertiary phosphine ligands by using Me3NO·2H2O as the decarbonylation reagent in 70% and 66% yields, respectively. The new complexes were characterized by means of elemental analysis, spectroscopy, and X-ray crystallography. Furthermore, the electrochemistry was studied by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Two diiron propane-1,2-dithiolate complexes with monosubstituted tris(3-chlorophenyl)phosphine or tris(4-trifluoromethylphenyl)phosphine were synthesized and characterized. Treatment of the parent complex [Fe2(CO)6{μ-SCH2CH(CH3)S}] (1) with tris(3-chlorophenyl)phosphine or tris(4-trifluoromethylphenyl)phosphine and Me3NO·2H2O as the decarbonylating agent afforded complexes [Fe2(CO)5P(3-C6H4Cl)3{µ-SCH2CH(CH3)S}] (2) and [Fe2(CO)5P(4-C6H4CF3)3{µ-SCH2CH(CH3)S}] (3) in 82% and 77% yields, respectively. Complexes 2 and 3 have been characterized by elemental analysis, IR, NMR spectroscopy, and X-ray diffraction analysis. Additionally, the electrochemical properties have been studied by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

Herein, we report the preparation and characterization of two diiron carbonyl complexes with ethyldiphenylphosphine or dicyclohexylphenylphosphine. Me3NO-driven decarbonylation of complex [Fe2(CO)6(µ-SCH2CH2CH2S)] (1) with the corresponding phosphine ligands afforded the products [Fe2(CO)5(Ph2PCH2CH3)(µ-SCH2CH2CH2S)] (2) and [Fe2(CO)5PhP(C6H11)2(µ-SCH2CH2CH2S)] (3) in 91% and 84% yields, respectively. The structures of complexes 2 and 3 have been identified by spectroscopy, elemental analysis, and X-ray diffraction analysis. Moreover, the electrochemistry was investigated by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

Treatment of the starting complex [Fe2(CO)6{μ-SCH2CH(CH2OH)S}] (1) with 2-(diphenylphosphino)benzoic acid in the presence of N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine gave the corresponding ester derivative [Fe2(CO)6{μ-SCH2CH(CH2O2CC6H4PPh2-2)S}] (2) in 92% yield. Further treatment of complex 2 with one equivalent of Me3NO · 2 H2O as the decarbonylating agent yielded diphenylphosphino-substituted complex [Fe2(CO)5{μ-SCH2CH(CH2O2CC6H4PPh2-2)S}] (3) in 79% yield. Both complexes were characterized by elemental analysis, spectroscopy, as well as by X-ray crystallography. Additionally, the electrochemical properties of these complexes were studied by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

In this article, two new binuclear iron compounds [Fe2(CO)5PPh(C6H11)2{µ-SCH2CH(CH2CH3)S}] (2) and [Fe2(CO)5PPh2(C6H11){µ-SCH2CH(CH2CH3)S}] (3), which can be regarded as the biomimics for the active site of [FeFe]-H2ases, have been synthesized by CO exchange of compound [Fe2(CO)6{μ-SCH2CH(CH2CH3)S}] (1) with cyclohexyldiph-enylphosphine or dicyclohexylphenylphosphine and their structures have been confirmed by spectroscopy, elemental analysis, and X-ray crystallography. They also exhibited good electrocatalytic activities for the generation of H2. [ABSTRACT FROM AUTHOR]

In this contribution, two diiron propane-1,3-dithiolate complexes with monosubstituted phosphine ligands have been synthesized and structurally characterized. Reactions of complex [Fe2(CO)6(µ-SCH2CH2CH2S)] (1) with a monophosphine ligand tri(m-tolyl)phosphine or tris(3-fluorophenyl)phosphine in the presence of Me3NO·2H2O as the CO-removing agent gave complexes 2 and 3 in 79% and 92% yields, respectively. Complexes 2 and 3 have been characterized by elemental analysis, IR, NMR spectroscopy, and X-ray diffraction analysis. Furthermore, the electrochemical properties of complexes 2 and 3 were studied by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

In this paper, three diiron butane-1,2-dithiolate complexes have been prepared and characterized. Treatment of the starting complex [Fe2(CO)6{µ-SCH2CH(CH2CH3)S}] (1) with a monophosphine ligand tris(2-thienyl)phosphine, tris(4-trifluoromethylphenyl)phosphine, or 4-(dimethylamino)phenyldiphenylphosphine and Me3NO·2H2O as the decarbonylating agent gave the target products 2‒4 in 75‒91% yields. These complexes have been characterized by elemental analysis, IR, NMR spectroscopy, as well as by X-ray crystallography. Moreover, the electrochemical properties of complexes 3 and 4 were investigated by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

Two diiron butane-1,2-dithiolate complexes containing tris(4-chlorophenyl)phosphine or tris(4-methoxyphenyl)phosphine have been prepared and characterized. Treatment of complex [Fe2(CO)6{μ-SCH2CH(CH2CH3)S}] (1) with tris(4-chlorophenyl)phosphine or tris(4-methoxyphenyl)phosphine in the presence of Me3NO · 2 H2O as the oxidizing agent gave the complexes [Fe2(CO)5{P(4-C6H4Cl)3}{µ-SCH2CH(CH2CH3)S)} (2) and [Fe2(CO)5{P(4-C6H4OCH3)3}{µ-SCH2CH(CH2CH3)S)}] (3) in 92% and 90% yields, respectively. Both complexes were characterized by elemental analysis, IR, NMR spectroscopy, and their structures were confirmed by single-crystal X-ray diffraction analysis. Moreover, the electrochemical properties of complexes 2 and 3 were investigated by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

Recently, graphene nanomaterials have attracted tremendous attention and have been utilized in various fields because of their excellent mechanical, thermal, chemical, optical properties, and good biocompatibility, especially in biomedical aspects. However, there is a concern that the unique characteristics of nanomaterials may have undesirable effects. Therefore, in this study, we sought to systematically investigate the effects of graphene quantum dots (GQDs) on the maturation of mouse oocytes and development of the offspring via in vitro and in vivo studies. In vitro, we found that the first polar body extrusion rate in the high dosage exposure groups (1.0–1.5 mg/ml) 2 decreased significantly and the failure of spindle migration and actin cap formation after GQDs exposure was observed. The underlying mechanisms might be associated with reactive oxygen species accumulation and DNA damage. Moreover, transmission electron microscope studies showed that GQDs may have been internalized into oocytes, tending to accumulate in the nucleus and severely affecting mitochondrial morphology, which included swollen and vacuolated mitochondria accompanied by cristae alteration with a lower amount of dense mitochondrial matrix. In vivo, when pregnant mice were exposed to GQDs at 8.5 days of gestation (GD, 8.5), we found that high dosage of GQD exposure (30 mg/kg) significantly affected mean fetal length; however, all the second generation of female mice grew up normal, attained sexual maturity, and gave birth to a healthy offspring after mating with a healthy male mouse. The results presented in this study are important for the future investigation of GQDs for the biomedical applications. [ABSTRACT FROM AUTHOR]

In this paper, five diiron propane-1,3-dithiolate complexes containing substituted phosphine ligands were prepared and structurally characterized. Treatment of [Fe2(CO)6(μ-SCH2CH2CH2S)] (1) with a monophosphine ligand methyl diphenylphosphinite, ethyl diphenylphosphinite, 4-(dimethylamino)phenyldiphenylphosphine, tris(2-methoxyphenyl)phosphine, or tris(4-chlorophenyl)phosphine in the presence of Me3NO·2H2O as the decarbonylating agent gave the corresponding phosphine-substituted analogues [Fe2(CO)5(L)(μ-SCH2CH2CH2S)] [L = Ph2POCH3, 2; Ph2POCH2CH3, 3; Ph2P(4-C6H4 NMe2), 4; P(2-C6H4OCH3)3, 5; P(4-C6H4Cl)3, 6] in 73–93% yields. Complexes 2–6 have been characterized by elemental analysis, spectroscopy, and X-ray crystallography. Additionally, electrochemical studies have shown that 2–6 can catalyze the reduction of protons to H2 in the presence of HOAc. [ABSTRACT FROM AUTHOR]

In this article, five diiron 1,2-dithiolate complexes containing phosphine ligands are reported. Treatment of complex [Fe2(CO)6(μ-SCH2CH2S)] (1) with the phosphine ligands tris(4-methylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(3-chlorophenyl)phosphine, tris(3-methylphenyl)phosphine, or 2-(diphenylphosphino)biphenyl in the presence of Me3NO·2H2O as the decarbonylating agent afforded the target products [Fe2(CO)5(L)(μ-SCH2CH2S)] [L = P(4-C6H4CH3)3, 2; P(4-C6H4OCH3)3, 3; P(3-C6H4Cl)3, 4; P(3-C6H4CH3)3, 5; Ph2P(2-C6H4Ph), 6] in 80–93% yields. Complexes 2–6 have been characterized by elemental analysis, spectroscopy, and X-ray crystallography. Additionally, the electrochemical properties were studied by cyclic voltammetry. [ABSTRACT FROM AUTHOR]

The reactions of the starting complex, [Fe2(CO)6{μ-SCH2CH (CH2CH3)S}] (1), with the phosphine ligands tris(4-methylphenyl)phosphine, diphenyl-2-pyridylphosphine, tris(4-fluorophenyl)phosphine, 2-(diphenylphosphino)benzaldehyde, or benzyldiphenylphosphine in the presence of the decarbonylating agent Me3NO·2H2O yielded the corresponding phosphine-substituted diiron butane-1,2-dithiolate complexes [Fe2(CO)5(L){μ-SCH2CH(CH2CH3)S}] (L = P(4-C6H4CH3)3, 2; Ph2P(2-C5H4N), 3; P(4-C6H4F)3, 4; Ph2P(2-C6H4CHO), 5; Ph2PCH2Ph, 6) in 75%–87% yields. The complexes have been characterized by elemental analysis, IR, 1H, and 31P{1H} NMR spectroscopy, as well as by single-crystal X-ray diffraction analysis. Moreover, the electrochemistry of 2–4 was studied by cyclic voltammetry, suggesting that they can catalyze the reduction of protons to H2 in the presence of HOAc. [ABSTRACT FROM AUTHOR]

Three diiron 1,2-dithiolate complexes with a trans-cinnamate ester have been characterized. Esterification of [Fe2(CO)6{μ-SCH2CH(CH2OH)S}] (1) with trans-cinnamic acid in the presence of N,N′-dicyclohexylcarbodiimide and 4-dimethylaminopyridine afforded [Fe2(CO)6[μ-SCH2CH(CH2O2CCH = CHPh)S}] (2) in 94% yield. Carbonyl substitution of 2 with a monophosphine ligand tris(4-fluorophenyl)phosphine or tris(2-methoxyphenyl)phosphine in the presence of Me3NO·2H2O resulted in formation of the corresponding monophosphine-substituted complexes [Fe2(CO)5 {P(C6H4F-4)3}{µ-SCH2CH(CH2O2CCH = CHPh)S}] (3) and [Fe2(CO)5{P (C6H4OCH3-2)3}{µ-SCH2CH(CH2O2CCH = CHPh)S}] (4) in 79% and 84% yields, respectively. Complexes 2-4 were structurally characterized by elemental analysis, spectroscopy and X-ray crystallography. Moreover, electrochemical properties of 2-4 were investigated. [ABSTRACT FROM AUTHOR]

In this paper, two diiron complexes have been prepared by CO exchange and structurally characterized. Treatment of complex [Fe2(CO)6{μ-SCH2CH(CH2O2CCH3)S}] (1) with diphenyl-2-pyridylphosphine in the presence of Me3NO·2H2O as the decarbonylating agent gave the corresponding monophosphine-substituted complex [Fe2(CO)5{Ph2P(2-C5H4N)}{μ-SCH2CH(CH2O2CCH3)S}] (2) in 85% yield. Similarly, complex [Fe2(CO)5{P(3-C6H4F)3}{μ-SCH2CH(CH2O2CPh)S}] (4) was obtained in 78% yield by the reaction of complex [Fe2(CO)6{μ-SCH2CH(CH2O2CPh)S}] (3) with tris(3-fluorophenyl)phosphine. The new complexes 2 and 4 have been characterized by elemental analysis, IR spectroscopy, NMR spectroscopy, as well as by X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

Abstract: The course of protein–lipid co‐oxidation was investigated in oil‐in‐water emulsions stabilized with proteins extracted from microwave‐treated (MWT) and conventional thermal‐treated (CTT) faba beans stored at 37°C for 7 days. Emulsions prepared with proteins from untreated (UT) faba beans and soy protein isolate (SP) were monitored for comparison. Lipid oxidation was detected through formation of primary and secondary oxidation products while protein oxidation was examined via tryptophan fluorescence degradation in interface and aqueous phase. Oxidation of proteins was more emphasized in the interfacial layers of MWT, CTT, and SP emulsions than in UT emulsions due to the prominence of radical chain‐driven co‐oxidation mechanism while lipoxygenase (LOX) activity in UT and MWT emulsions resulted in high amounts of hydroperoxides and abundance in lipid oxidation volatiles. Conventional thermal treatment provided better oxidative stability than microwave treatment reflected in lower levels of hydroperoxides and relative lack of diversity in lipid volatiles. Among detected volatiles, formation of ketones was more distinguished in MWT, CTT, and SP emulsions while UT emulsions contained a more diverse range of alkenals and alkanals. Ketones are known to form mainly through radical recombination reactions which combined with the results of protein oxidation supports that radical transfer reactions between proteins and lipids were the driving force behind oxidation in MWT, CTT, and SP emulsions. Treatments of faba beans resulted in increased oxidative stability of emulsified lipids and lower degradation of aqueous phase proteins. [ABSTRACT FROM AUTHOR]

Herein, electrospinnability of perfluorosulfonic acid (PFSA)–polyvinylidene fluoride (PVDF) blends with different ratios of PVDF were investigated in detail. A well-formed nanofiber structure can be obtained only when the minimum ratio of PVDF in the blend reaches 9%. The reason was explained by the change in the properties, such as viscosity, conductivity, and surface tension, and interconnected aggregates in the blend solutions as revealed by dynamic light scattering (DLS) and the viscoelasticity behavior. After this, the property and morphology of the PFSA–PVDF nanofibers were investigated. SEM images showed that the average diameter of the nanofibers ranged from 75 to 170 nm. Small-angle X-ray scattering (SAXS) and DSC results showed that the microstructure of PFSA and the crystallization of PVDF in the nanofiber interfered with each other, which was attributed to the interaction between the backbone of PFSA and PVDF. CA and IEC revealed that the nanofibers were highly hydrophobic. Finally, the PFSA–PVDF nanofiber membranes were evaluated as a catalyst in the esterification reaction and as a separator in Li-ion battery. It was found that PFSA/PVDF nanofiber membrane with high PFSA ratio showed higher capacity and more stable cycle performance after 100 cycles as compared to the PVDF nanofiber, which could be used as a separator in Li-ion battery. [ABSTRACT FROM AUTHOR]

Food-use of faba bean has been commonly limited by the unpleasant “beany flavour” that can be induced by untreated beans. Pre-treatment of faba beans with microwave heating for different durations and with conventional oven heating was investigated, in order to resolve the “beany flavour” problem. Heating the seeds by microwave for 1.5 min at 950 W was found to be an optimum pre-treatment method that effectively inactivated the endogenous peroxidase and lipoxygenase, which are responsible for the beany flavour causation. In addition, the treatment improved the technological properties of the beans as it decreased seed hardness, improved milling quality, and increased flour pasting viscosity. It slightly decreased protein solubility, while heating with microwave for 2 min or longer decreased the protein solubility more severely and decreased the flour pasting viscosity. Conventional oven heating at 170 °C for 30 min also inactivated the peroxidase and lipoxygenase. The microstructure of the particles in flour-water-suspension was changed by both microwave and conventional oven heating methods, which induced the formation of water-insoluble starch-protein aggregates. Microwave heating for 1.5 min provided an excellent balance of improved milling properties, preserved protein solubility and minimized activity of enzymes that are detrimental to product flavour. [ABSTRACT FROM AUTHOR]

Reactions of (μ-edt)Fe2(CO)6(edt = SCH2CH2S) (1) with the monophosphine ligands Ph2PCH2Ph, Ph2PC6H11, Ph2PCH2CH2CH3, or P(2-C4H3O)3in the presence of Me3NO∙2H2O afforded (μ-edt)Fe2(CO)5L [L = Ph2PCH2Ph,2; Ph2PC6H11,3; Ph2PCH2CH2CH3,4; P(2-C4H3O)3,5] in 70–88% yields. Complexes2–5were characterized by spectroscopy and single crystal X-ray diffraction analysis. The phosphorus of2–5is in an apical position of the distorted octahedral geometry of iron. [ABSTRACT FROM PUBLISHER]

Oat protein produced by a dry milling process was enzymatically deamidated by a food-grade protein-glutaminase (PG), and the effects on structure, solubility and emulsifying properties of oat proteins were studied. The reactions were conducted at neutral pH and low salt concentration conditions. Oat proteins were deamidated up to a deamidation degree of 59%. The solubility of proteins doubled. Oil-in-water emulsions prepared with the native and deamidated oat proteins differed as the emulsions prepared from oat proteins with high deamidation degree had a more uniform oil droplet particle size and longer stability. Fourier transform infrared (FT-IR) analysis demonstrated that oat protein secondary structure became more flexible by deamidation. Protein-glutaminase mediated deamidation appeared to be a promising technique to improve oat protein functionality such as emulsifying ability and solubility. [ABSTRACT FROM AUTHOR]

Faba bean protein has good functionalities, but it is little used in the food industry. This study identified a challenge from unfavourable starch gelation when utilizing faba bean for producing protein-based emulsion gel foods, and developed processing methods to overcome that. Two types of protein-based emulsion gel foods, namely yogurt and tofu analogue products, were prepared. The processing methods in this study involved steps of thermal pre-treatment of the beans, dehulling, milling, adding plant oil, homogenization, prevention of starch gelation, and inducing protein gelation. Two methods for preventing starch gelation were studied, namely starch removal and hydrolysis. The gel texture, water-holding capacity, and structural properties of the gel products were evaluated. Both starch-gelation prevention methods produced yogurt and tofu analogue products having typical emulsion gel properties. Hydrolysis of starch was favourable for producing the yogurt analogue, because the hydrolysate compounds improved the gel strength and viscosity. Moreover, it utilized the whole flour, meaning all the nutrients from the cotyledon were used and no side-stream was created. In contrast, starch removal was slightly better than hydrolysis for producing the tofu analogue, because the hydrolysate lowered the gel strength and water-holding capacity of the products. It is both possible and ecologically sustainable to utilize whole faba bean flour for making emulsion gel products. [ABSTRACT FROM AUTHOR]

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 [Fe2(CO)6{μ‐SCH2CH(CH3)S}] (1) with a monophosphine ligand tris(4‐methylphenyl)phosphine, diphenyl‐2‐pyridylphosphine, tris(4‐chlorophenyl)phosphine, triphenylphosphine, or tris(4‐fluorophenyl)phosphine in the presence of the oxidative agent Me3NO·2H2O gave the monophosphine‐substituted diiron complexes [Fe2(CO)5(L){μ‐SCH2CH(CH3)S}] [L = P(4‐C6H4CH3)3, 2; Ph2P(2‐C5H4N), 3; P(4‐C6H4Cl)3, 4; PPh3, 5; P(4‐C6H4F)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 H2 in the presence of HOAc. [ABSTRACT FROM AUTHOR]

Six diiron ethanedithiolate complexes containing benzoate ester have been synthesized and characterized. Treatment of the starting material [{μ‐SCH2CH(CH2OH)S}Fe2(CO)6] (1) with benzoic acid in the presence of N,N′‐dicyclohexylcarbodiimide and 4‐dimethylaminopyridine afforded the benzoate ester‐containing complex [{μ‐SCH2CH(CH2O2CPh)S}Fe2(CO)6] (2) in 97% yield. Carbonyl substitution of complex 2 with a monophosphine ligand, such as triphenylphosphine, tris(2‐methoxyphenyl)phosphine, tris(4‐fluorophenyl)phosphine, isopropyldiphenylphosphine or cyclohexyldiphenylphosphine, in the presence of Me3NO⋅2H2O gave the derivatives [{μ‐SCH2CH(CH2O2CPh)S}Fe2(CO)5L] (L = PPh3, 3; P(C6H4OCH3‐2)3, 4; P(C6H4F‐4)3, 5; Ph2PCH(CH3)2, 6; Ph2PC6H11, 7) in 66–95% yields. Complexes 2–7 were characterized using elemental analysis, spectroscopy and X‐ray diffraction analysis. In addition, these complexes can catalyze the reduction of protons to H2 in the presence of weak acid HOAc under electrochemical conditions. Six diiron complexes were prepared by esterification or carbonyl substitution and structurally characterized using elemental analysis, infrared and NMR spectroscopies and X‐ray crystallography. In addition, the electrochemical properties of the complexes were studied using cyclic voltammetry. [ABSTRACT FROM AUTHOR]

Graphical abstract Five diiron ethanedithiolate complexes [Fe 2 (CO) 5 (L){μ-SCH 2 CH(CH 2 O 2 CCH 3)S}] (L = P(2-C 4 H 3 O) 3 , 2 ; P(2-C 4 H 3 S) 3 , 3 ; P(4-C 6 H 4 F) 3 , 4 ; P(4-C 6 H 4 Cl) 3 , 5 ; Ph 2 PC 6 H 11 , 6) containing acetate ester and phosphine ligands were prepared by CO substitution. The complexes 2 – 6 have been characterized by elemental analysis, IR and NMR spectra, as well as by X-ray crystallography. Moreover, the electrochemical properties were also studied. Abstract A series of acetate ester containing diiron ethanedithiolate complexes have been synthesized and structurally characterized. CO substitution of complex [Fe 2 (CO) 6 {μ-SCH 2 CH(CH 2 O 2 CCH 3)S}] (1) with the phosphine ligands tris(2-furyl)phosphine, tris(2-thienyl)phosphine, tris(4-fluorophenyl)phosphine, tris(4-chlorophenyl)phosphine, or cyclohexyldiphenylphosphine in the presence of the decarbonylating agent Me 3 NO·2H 2 O gave the phosphine-substituted diiron derivatives [Fe 2 (CO) 5 (L){μ-SCH 2 CH(CH 2 O 2 CCH 3)S}] (L = P(2-C 4 H 3 O) 3 , 2 ; P(2-C 4 H 3 S) 3 , 3 ; P(4-C 6 H 4 F) 3 , 4 ; P(4-C 6 H 4 Cl) 3 , 5 ; Ph 2 PC 6 H 11 , 6) in 86–95% yields. The complexes 2 – 6 have been characterized by elemental analysis, spectroscopy, and X-ray diffraction analysis. Additionally, the electrochemical properties were investigated by cyclic voltammetry. [ABSTRACT FROM AUTHOR]