Reactivity of Hydroxy and Amino Derivatives of 2‐Phenyl‐1H‐imidazoline and 2‐Phenyl‐1H‐imidazole toward Isocyanates: Synthesis of Appropriate Carbamates and Ureas

Reactivity of 2‐(4‐hydroxyphenyl)‐1H‐imidazoline and 2‐(4‐hydroxyphenyl)‐1H‐imidazole toward substituted phenyl isocyanates was studied. When mentioned imidazoline was treated with 2.5 equiv of substituted phenyl isocyanate, three N,O‐dicarboxamides were prepared (substituents are H, 4‐NO₂, and 4‐CH₃). Subsequently, N,O‐diacetylated 2‐(4‐hydroxyphenyl)‐1H‐imidazoline was prepared and selective deprotection method was developed for preparation of 1‐acetyl‐2‐(4‐hydroxyphenyl)‐1H‐imidazoline using diethylamine in acetone. Six carbamates derived from this imidazoline were then prepared using 1.1 equiv of substituted phenyl isocyanates (substituents are H, 4‐CH₃, 4‐OCH₃, 4‐NO₂, 4‐CN, and 3‐CF₃). Finally, two carbamates were prepared from 2‐(4‐hydroxyphenyl)‐1H‐imidazole (substituents are 4‐NO₂ and 4‐CN). No reactivity to imidazole ring was observed in this case. Eight derivatives were subjected to antimycobacterial screening. Concurrently, reactivity of 2‐(2‐aminophenyl)‐ and 2‐(2‐hydroxyphenyl)‐1H‐imidazole toward aliphatic and aromatic isocyanates was studied. Eight ureas were prepared using equivalent mixture of 2‐(2‐aminophenyl)‐1H‐imidazole and isocyanate (Et, Pr, isoPr, terc‐Bu, Cy, Ph, 4‐CH₃C₆H₄, 4‐CNC₆H₄). Similar attempts to obtain related carbamates from 2‐(2‐hydroxyphenyl)‐1H‐imidazole lead only to three substituted phenyl carbamates (substituents are 4‐CH₃, 4‐NO₂, and 4‐CN). In both cases, no reactivity to imidazole ring was observed again.     

Application of π‐Extended Ferrocene with Varied Anchoring Groups as Photosensitizers in TiO2‐Based Dye‐Sensitized Solar Cells (DSSCs)

Two new compounds, FcCHNC₆H₄COOH ( 1 ) and FcCHNCH₂CH₂OH ( 2 ) (Fc=C₅H₄FeC₅H₅), have been synthesized and characterized by elemental analyses, IR and ¹H NMR spectroscopy, and ESI‐MS. Attempt has been made to explain their quasi‐reversible redox behavior evidenced by cyclic voltammetry using density functional theory (DFT) calculations. Light‐harvesting properties of both the compounds and also the starting material, FcCHO ( 3 ), have been studied using these compounds as photosensitizers in TiO₂‐based dye‐sensitized solar cells having either a propylene carbonate‐based electrolyte or ionic liquid electrolyte, namely, 1‐propyl‐3‐methyl imidazolium iodide (PMII). Long‐term stability of the photocurrent output of the cell using compound 1 as photosensitizer has been monitored periodically over 1400 h.     

Metal–Organic Gel Material Based on UiO‐66‐NH2 Nanoparticles for Improved Adsorption and Conversion of Carbon Dioxide

Metal–organic frameworks (MOFs) including the UiO‐66 series show potential application in the adsorption and conversion of CO₂. Herein, we report the first tetravalent metal‐based metal–organic gels constructed from Zr^IV and 2‐aminoterephthalic acid (H₂BDC‐NH₂). The ZrBDC‐NH₂ gel materials are based on UiO‐66‐NH₂ nanoparticles and were easily prepared under mild conditions (80 °C for 4.5 h). The ZrBDC‐NH₂‐1:1‐0.2 gel material has a high surface area (up to 1040 m² g^?1) and showed outstanding performance in CO₂ adsorption (by using the dried material) and conversion (by using the wet gel) arising from the combined advantages of the gel and the UiO‐66‐NH₂ MOF. The ZrBDC‐NH₂‐1:1‐0.2 dried material showed 38 % higher capture capacity for CO₂ at 298 K than microcrystalline UiO‐66‐NH₂. It showed high ideal adsorbed solution theory selectivity (71.6 at 298 K) for a CO₂/N₂ gas mixture (molar ratio 15:85). Furthermore, the ZrBDC‐NH₂‐1:1‐0.2 gel showed activity as a heterogeneous catalyst in the chemical fixation of CO₂ and an excellent catalytic performance was achieved for the cycloaddition of atmospheric pressure of CO₂ to epoxides at 373 K. In addition, the gel catalyst could be reused over multiple cycles with no considerable loss of catalytic activity.     

Complete experimental and theoretical proton and carbon nuclear magnetic resonance spectral assignments,molecular structure and conformational study of 1‐cyclohexylpiperazine and 1‐(4‐pyridyl)piperazine

The possible stable forms and molecular structures of 1‐cyclohexylpiperazine (1‐chpp) and 1‐(4‐pyridyl)piperazine (1‐4pypp) molecules have been studied experimentally and theoretically using nuclear magnetic resonance(NMR) spectroscopy. ¹³C, ¹⁵N cross‐polarization magic‐angle spinning NMR and liquid phase¹H, ¹³C, DEPT, COSY, HETCOR and INADEQUATE NMR spectra of 1‐chpp (C₁₀H₂₀N₂) and 1‐4pypp (C₉H₁₃N₂) have been reported. Solvent effects on nuclear magnetic shielding tensors have been investigated using CDCl₃, CD₃ OD, dimethylsulfoxide (DMSO)‐d₆, (CD₃)₂CO, D₂O and CD₂Cl₂. ¹H and ¹³C NMR chemical shifts have been calculated for the most stable two conformers, equatorial–equatorial (e–e) and axial–equatorial (a–e) forms of 1‐chpp and 1‐4pypp using B3LYP/6‐311++G(d,p)//6‐31G(d) level of theory. Results from experimental and theoretical data showed that the molecular geometry and the mole fractions of stable conformers of both molecules are solvent dependent. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and characterization of Mannich base monophenolate lanthanide complexes and their application in ring‐opening polymerization of ε‐caprolactone

A series of Mannich base monophenol ligands [2,4‐^tBu₂‐6‐CH₂NMe₂‐PhOH ( HA ), 2,4‐^tBu₂‐6‐CH₂NEt₂‐PhOH ( HB ), 2,4‐^tBu₂‐6‐CH₂Py‐PhOH ( HC ), 2‐^tBu‐4‐Me‐6‐CH₂Py‐PhOH ( HD ), 4‐^tBu‐2,6‐(CH₂Py)₂‐PhOH ( HE )] were synthesized by Mannich reaction using phenol and formaldehyde reacting with secondary amine. A series of homoleptic lanthanide complexes [LaA₃ ( 1 ), GdA₃ ( 2 ), LaB₃ ( 3 ), GdB₃ ( 4 ), LaC₃ ( 5 ), GdC₃ ( 6 ), LaD₃ ( 7 ), GdD₃ ( 8 ), LaE₃ ( 9 ), GdE₃ ( 10 )] were prepared by amine elimination reactions of the ligands with Ln[N(SiMe₃)₂]₃ (Ln = La, Gd). Complexes 1 , 3 , 5 , 7 and 9 were all characterized using NMR spectra, and the structures of complexes 3 and 5 were determined using single‐crystal X‐ray diffraction. Complexes 3 and 5 are isostructural, and the lanthanum center exhibits a distorted octahedral geometry, in which the O(1), O(2) and O(3) atoms occupy three positions and N(1), N(2) and N(3) atoms occupy the other three positions. All complexes were characterized using elemental analysis and infrared spectra. The catalytic properties of complexes 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 for the ring‐opening polymerization of ε‐caprolactone were studied, and the results show that all complexes are efficient initiators for this ring‐opening polymerization reaction. Copyright © 2016 John Wiley & Sons, Ltd.     

Oxazoline chemistry part III. Synthesis and characterisation of [2‐(2′‐anilinyl)‐2‐oxazolines] and some related compounds

The syntheses and characterisation of a series of chiral and achiral 2‐(aminophenyl)‐2‐oxazolines and some related compounds is reported. All of the derivatives have been produced by a one‐step procedure involving the treatment of isatoic anhydride (i.e. [2H]‐3, 1‐benzoxazine‐[1H‐2,4‐dione: 1 ) or its 5‐chloro analogue with a slight excess of appropriate amino‐alcohols. In most cases, anhydrous ZnCl₂ is shown to be an effective Lewis acid catalyst for this reaction at reflux temperature in high boiling aromatic solvents (PhCl or PhMe). Oxazolines have been readily formed using rac‐2‐amino‐1‐butanol, (S)‐phenylglycinol, 2‐methyl‐2‐amino‐1‐propanol and (1S,2R) or (IR,2S)‐cis‐ 1 ‐amino‐2‐indanol; yields range from 85% to 22%. The use of aminoalcohols such as 2‐ethanolamine, (±)‐2‐amino‐1‐phenyl‐1‐propanol or 3‐amino‐1‐propanol (to give the corresponding 4,5‐dihydro‐1,3‐oxazine) results in poor yields. The use of other Lewis acid catalysts (silicic acid, Cd(acac)₂·2H₂O, CuCl₂·2H₂O, InCl₃) or higher temperatures did not improve the yields with these latter two substrates. Benzoxazoles and N‐substituted benzoxazoles can also be obtained in reasonable yields from 1 using 2‐aminophenol (36%) or 2‐amino‐3‐hydroxypyridine (45%).     

Investigation the chemical reactivity of positions N‐3, C‐5 and C6‐methyl group in biginelli type compounds and synthesis of new dihydropyrimidine derivatives

The compounds 5‐ethoxycarbonyl‐1,6‐dimethyl‐4‐(3‐nitrophenyl)‐3,4‐dihydropyrimidin‐2(lH)‐one (5) and 5‐ethoxycarbonyl‐1‐phenyl‐6‐methyl‐4‐(3‐nitrophenyl)‐3,4‐dihydropyrimidin‐2(lH)‐one (1) were prepared by the Biginelli condensation method and they converted to eight N‐3 substituted dihydropyrimidines using NaH and various electrophiles (ClCO₂Et, TsCl, Ac₂O, AcCl and PhCOCl). Compound (1) was mono‐brominated at the C₆‐methyl group using bromine solution. Reaction of the bromo derivative with amino nucleophiles such as methyl amine and cyclohexyl amine produced two pyrrolo‐pyrimidine derivatives. All the compounds except 5‐ethoxycarbonyl‐1‐phenyl‐6‐methyl‐4‐(3‐nitrophenyl)‐3,4‐dihydropyrimidin‐2(l_H)‐one ( 4 ) were purified by recrystallization methods. The structure of all the new compounds was confirmed using FT‐ir,¹H nmr, ¹³C nmr spectral and elemental analyses methods.     

High-throughput and time-resolved energy-dispersive X-ray diffraction (EDXRD) study of the formation of CAU-1-(OH)2: microwave and conventional heating

Aluminium dihydroxyterephthalate [Al₈(OH)₄(OCH₃)₈(BDC(OH)₂)₆] ? x H₂O (denoted CAU‐1‐(OH)₂) was synthesized under solvothermal conditions and characterized by X‐ray powder diffraction, IR spectroscopy, sorption measurements, as well as thermogravimetric and elemental analysis. CAU‐1‐(OH)₂ is isoreticular to CAU‐1 and its pores are lined with OH groups. It is stable under ambient conditions and in water, and it exhibits permanent porosity and two types of cavities with effective diameters of approximately 1 and 0.45 nm. The crystallization of CAU‐1‐(OH)₂ was studied by in situ energy‐dispersive X‐ray diffraction (EDXRD) experiments in the 120–145 °C temperature range. Two heating methods—conventional and microwave—were investigated. The latter leads to shorter induction periods as well as shorter reaction times. Whereas CAU‐1‐(OH)₂ is formed at all investigated temperatures using conventional heating, it is only observed below 130 °C using microwave heating. The calculation of the activation energy of the crystallization of CAU‐1‐(OH)₂ exhibits similar values for microwave and conventional synthesis.     

Synthesis and characterization of (pyrazolylethylphosphinite)nickel(II) complexes and catalytic activity towards ethylene oligomerization

Compounds (2‐(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)ethyldiphenylphosphinite ( L1 ), 2‐(3,5‐di‐tert‐butyl‐1H‐pyrazol‐1‐yl)ethyldiphenylphosphinite ( L2 ) , and 2‐(3,5‐diphenyl‐1H‐pyrazol‐1‐yl)ethyldiphenylphosphinite ( L3 ) were prepared using the synthetic routes reported in literature. These compounds were reacted with [NiCl₂(DME)₂] or [NiBr₂(DME)₂] under appropriate reaction conditions to afford six new nickel(II) compounds ([NiCl₂( L1)] ( 1 ), [NiCl₂( L2 )] ( 2 ), [NiCl₂( L3 )] ( 3 ), [NiBr₂( L1 )] ( 4 ), [NiBr₂( L2 )] ( 5 ) and [NiBr₂( L3 )] ( 6 )). The new nickel(II) pre‐catalysts catalyze the oligomerization of ethylene, in the presence of ethylaluminium dichloride as co‐catalyst, to produce butenes, hexenes, octenes and higher carbon chain ethylene oligomers with very little Friedel‐Crafts alkylation products when the reactions were run in toluene.     

Two two‐dimensional supramolecular copper(II) and cobalt(III) complexes derived from a new quinazoline‐type ligand: Syntheses,structures, and spectral,thermal, electrochemical and antimicrobial activity studies

Two two‐dimensional supramolecular copper(II) and cobalt(III) complexes, Cu(L¹)₂ ( 1 ; HL¹ = 2‐hydroxy‐3‐methoxybenzaldehyde oxime) and [Co(L²)₂]₂⋅2CH₃COOCH₂CH₃ ( 2 ; HL² = 1‐(2‐{[(E )‐3‐methoxy‐2‐hydroxybenzylidene]amino}phenyl)ethanone oxime), have been synthesized via complexation of Cu(II) nitrate trihydrate and Co(II) acetate tetrahydrate with HL. A plausible reaction mechanism for the formation of HL¹ is proposed. HL was synthesized and characterized using infrared, ¹H NMR and ¹³C NMR spectra, as well as elemental analysis. Complexes 1 and 2 were investigated using single‐crystal X‐ray diffraction and have a 2:1 ligand‐to‐metal ratio. Different geometric features of both complexes are observed. In their crystal structures, 1 and 2 form infinite two‐dimensional structures and 2 forms a three‐dimensional supramolecular framework. Electron paramagnetic resonance spectra of 1 and 2 were also investigated. Moreover, thermal and electrochemical properties and antimicrobial activity of 2 were also studied. In addition, the calculated HOMO and LUMO energies show the character of complex 1 .     

5‐(1,2,3‐Triazol‐1‐yl)tetrazole Derivatives of an Azidotetrazole via Click Chemistry

N? C bonded (non‐bridged) 5‐(1,2,3‐triazol‐1‐yl)tetrazoles were synthesized by the Cu^I‐catalyzed 1,3‐dipolar azide–alkyne cycloaddition click reaction using 5‐azido‐N‐(propan‐2‐ylidene)‐1H‐tetrazole ( 1 ). For example, the click reaction of 1 in the presence of CuSO₄?5 H₂O and Na ascorbate at 65–70 °C for 48 h in CH₃CN/H₂O co‐solvent was found to be limited to only terminal alkynes that have electron‐withdrawing groups, CF₃C?CH ( 2 a ) and SF₅C?CH ( 2 b ), giving rise to isopropylidene‐[5‐(4‐trifluoromethyl‐1,2,3‐triazol‐1‐yl)tetrazol‐1‐yl]amine ( 3 a ) and isopropylidene‐[5‐(4‐pentafluorosulfanyl‐1,2,3‐triazol‐1‐yl)tetrazol‐1‐yl]amine ( 3 b ) in 47 % and 66 % yields, respectively. When carried out under conditions using CuI and 2,6‐lutidine as catalysts at 0 °C for 13 h in CHCl₃, the click reaction was versatile toward alkynes even those having electron‐donating groups. Properties of new products were determined and compared with those of 1 . Heats of formation, detonation pressures, detonation velocities and impact sensitivities are reported for these new 5‐(1,2,3‐triazol‐1‐yl)tetrazoles.     

Two silver(I) complexes with bis(benzimidazole)‐2‐oxopropane ligands: Syntheses,crystal structures and DNA binding studies

Two Ag(I) complexes, [Ag₂(bobb)₂]⋅(NO₃)₂ ( 1 ) and [Ag₂(crotonate)₂(aobb)]_n ( 2 ) (bobb =1,3‐bis(1‐benzylbenzimidazol‐2‐yl)‐2‐oxapropane; aobb =1,3‐bis(1‐allylbenzimidazol‐2‐yl)‐2‐oxopropane), have been synthesized and characterized using elemental analysis, electrical conductivities, infrared and UV–visible spectral measurements and single‐crystal X‐ray diffraction. Complex 1 is binuclear and three‐coordinated by two N atoms from two bobb ligands, while complex 2 is a unique metal organic compound with diamond‐like multinuclear Ag centers with each Ag bridged by two aobb ligands and two crotonate ions to form one‐dimensional single polymer chain structures and extended into two‐dimensional frameworks through π–π and intermolecular C─H⋅⋅⋅O hydrogen bonds. The adjacent Ag(I) centers are bridged by allyl from aobb which is not only a σ‐bonding ligand, but also a π‐acid ligand. The DNA binding modes of complexes 1 and 2 were investigated using electronic absorption titration, fluorescence spectra and viscosity measurements. The results suggest that the two complexes bind to DNA via an intercalative mode, and their binding affinity for DNA follows the order 2  >  1 . This is due to the chelating effects which can enhance the planar functionality of the metal complexes.     

Copper‐catalyzed Synthesis of N‐alkylated 2‐(4‐substituted‐1H‐1,2,3‐triazol‐1‐yl)‐1H‐indole‐3‐carbaldehyde by Step‐wise and One‐pot Three‐component Huisgen's 1,3‐dipolar Cycloaddition Reaction

An efficient method for the synthesis of N‐alkylated 2‐(4‐substituted‐1H‐1,2,3‐triazol‐1‐yl)‐1H‐indole‐3‐carbaldehyde has been developed starting from oxindole and indole using Huisgen's 1,3‐dipolar cycloaddition reaction of organic azides to alkynes. The effect of catalysts and solvent on these reactions has been investigated. Among all these conditions, while using CuSO₄·5H₂O, DMF was found to be the best system for this reaction. It could also be prepared in a one‐pot three‐component manner by treating equimolar quantities of halides, azides, and alkynes. The Huisgen's 1,3‐dipolar cycloaddition reaction was performed using CuSO₄·5H₂O in DMF with easy work‐up procedure.     

A Sequential Method to Prepare Polymorphs and Solvatomorphs of [Fe(1,3‐bpp)2](ClO4)2⋅nH2O (n=0, 1, 2) with Varying Spin‐Crossover Behaviour

Two polymorphs of the spin crossover (SCO) compound [Fe(1,3‐bpp)₂](ClO₄)₂ ( 1 and 2 ; 1,3‐bpp=2‐(pyrazol‐1‐yl)‐6‐(pyrazol‐3‐yl)pyridine) were prepared using a novel, stepwise procedure. Crystals of 1 deposit from dry solvents, while 2 is obtained from a solid‐state procedure, by sequentially removing lattice H₂O molecules from the solvatomorph [Fe(1,3‐bpp)₂](ClO₄)₂?2 H₂O ( 2 ?2 H₂O), using single‐crystal‐to‐single‐crystal (SCSC) transformations. Hydrate 2 ?2 H₂O is obtained through the same reaction as 1 , now with 2.5 % of water added. Compounds 2 and 2 ?2 H₂O are unstable in the atmosphere and absorb or lose one equivalent of water, respectively, to both yield the stable solvatomorph [Fe(1,3‐bpp)₂](ClO₄)₂?H₂O ( 2 ?H₂O), also following SCSC processes. The four derivatives have been characterised by single‐crystal X‐ray diffraction (SCXRD). Furthermore, the homogeneity of the various compounds as well as their SCSC interconversions have been confirmed by powder X‐ray diffraction (PXRD). Polymorphs 1 and 2 exhibit abrupt SCO behaviour near room temperature with T_1/2↑=279/316 K and T_1/2↓=276/314 K (near 40 K of shift) and different cooperativity.     

Synthesis of Thieno[2,3‐b]quinolinone Derivatives

The Knoevenagel reactions of malononitrile with acetophenone or 4‐substituted acetophenons were carried to give the corresponding 2‐(1‐aryle thylidene)malononitriles, which was further cyclized with sulfur using NaHCO₃ as catalysts to generate 2‐amino‐5‐arylthiophene‐3‐carbonitrile 2 . The intermediate enamines 3 were prepared by refluxing of 2 with 5‐substituted‐1,3‐cyclohexanedione using p‐toluenesulfonic acid as catalyst. The title compounds 4‐amino‐3‐aryl ‐7‐substituted‐7,8‐dihydrothieno[2,3‐b]quinolin‐5(6H)‐one were synthesized by cyclization of 3 in the presence of K₂CO₃ and Cu₂Cl₂. The structures of all compounds were characterized by elemental analysis, IR, MS, and ¹H‐NMR spectra.     

Synthesis of 6‐Aminoindolo[2,1‐a]isoquinoline‐5‐carbonitriles by the Cu‐Catalyzed Reaction of 2‐(2‐Bromophenyl)‐1H‐indoles with CH2(CN)2

A series of 6‐aminoindolo[2,1‐a]isoquinoline‐5‐carbonitriles 4 have been prepared by treatment of 2‐(2‐bromophenyl)‐1H‐indoles 1 , available from 1‐(2‐bromophenyl)ethanones or 1‐(2‐bromophenyl)propan‐1‐ones by using Fischer indole synthesis, with propanedinitrile in the presence of a catalytic amount of CuBr and an excess of K₂CO₃ in DMSO at 100°.     

Synthesis and Characterization of Benzochromeno[2,3‐b]tetrahydroquinolinone Derivatives

We report on a novel method for the preparation of a new series of benzochromeno[2,3‐b]tetrahydroquinolin‐1‐one derivatives. The title compounds are prepared by the 5‐substituted‐1,3 ‐cyclohexanedione and 3‐amino‐1‐aryl‐1H‐benzo[f]chromene‐2‐carbonitrile or 2‐amino‐4‐aryl‐4H‐benzo[h]chromene‐3‐carbonitrile using dilute HCl, K₂CO₃, and Cu₂Cl₂ as catalysts. The method has the advantages of simple operation, high efficiency, and low toxicity. The structures of all compounds are characterized by elemental analysis, IR, MS, and ¹H NMR spectra. Two single crystals are characterized by using X‐ray diffraction.     

Low‐Valent Ruthenium Induced Simultaneous Reduction of Nitro Group and C‐C Double Bond in Nitroolefin 1‐Phenyl‐2‐Nitropropene‐1

The reduction of 1‐phenyl‐2‐nitropropene‐1 ( 1 ) on using ruthenium complexes was studied in detail in order to correlate this method with those previously recorded in the literature for the hydrogenation of nitroolefins. A variety of products was isolated by varying the reaction temperature and solvent. Among them was 1‐phenyl‐2‐propylamine ( 4 ), completely reduced from the selective both double bond and nitro group. 1‐Phenyl‐2‐propanol ( 5 ) was observed due to reduction of phenylacetone at 125 °C in the presence of ruthenium catalyst. When reaction temperature was lower than 125 °C, by employing RuCl₂(PPh₃)₃ complex, 1‐phenyl‐2‐nitropropane ( 2 ) and phenylacetone ( 3 ) were obtained, respectively. Ru‐BINAP complexes were attempted to produce chiral amine from starting material 1‐phenyl‐2‐nitropropene‐1 ( 1 ).     

Selective oxidation of benzyl alcohol to benzaldehyde, 1‐phenylethanol to acetophenone and fluorene to fluorenol catalysed by iron (II) complexes supported by pincer‐type ligands: Studies on rapid degradation of organic dyes

Hexacoordinated non‐heme iron complexes [Fe^II(L¹)₂](ClO₄)₂ ( 1 ) and [Fe^II(L²)₂](PF₆)₂ ( 2 ) have been synthesized using ligands L¹ = (E)‐2‐chloro‐6‐(2‐(pyridin‐2ylmethylene) hydrazinyl)pyridine and L² = (E)‐2‐chloro‐6‐(2‐(1‐(pyridin‐2‐yl)ethylidene)hydrazinyl) pyridine]. These complexes are highly active non‐heme iron catalysts to catalyze the C (sp³)?H bonds of alkanes. These iron complexes have been characterized using ESI?MS analysis and molecular structures were determined by X‐ray crystallography. ESI ? MS analysis also helped to understand the generation of intermediate species like Fe^III?OOH and Fe^IV=O. DFT and TD?DFT calculations revealed that the oxidation reactions were performed through high‐valent iron center and a probable reaction mechanism was proposed. These complexes were also utilized for the degradation of orange II and methylene blue dyes.     

Synthesis and properties of m‐ferrocenylbenzoylthiadiazole derivatives

A series of m‐ferrocenylbenzoylthiadiazole compounds, namely FcL₁–FcL₇, were synthesized using 3‐ferrocenylbenzoic acid and 2‐amino‐5‐aryl‐1,3,4‐thiadiazole as raw materials. These compounds were characterized using infrared and NMR spectroscopies and elemental analysis. The crystal structure of FcL₇ was determined using X‐ray diffraction. The electrochemical behaviors of FcL₁–FcL₇ revealed that the redox reactions on the surface of electrodes were reversible with a single‐electron mechanism. Also, FcL₁–FcL₇ demonstrated certain redox responses to Pb²⁺ and Zn²⁺. Moreover, FcL₅–FcL₇ exhibited good inhibition against human esophageal cancer cells in anticancer activity tests.