Electrooxdation of Tricarbonyl(N,N-Diphenylcyclohexadienecarboxamide)Iron Complexes. Reversibility of Electron Transfer and Free Energy Change

Qualitative and quantitative criteria of irreversibility of electron transfer in cyclic voltammetry (CV) of tricarbonyl(N,N-diphenylcyclohexadienecarboxamide)iron complexes were investigated. The measurement of the heterogeneous rate constants for electron transfer according to CV data over an extended range of free energy change ( ΔG) for these complexes are described. Kinetic analyses of the electrochemical technique demonstrates that when the applied potential exceeds the standard potential E°, the experimental rate constant k_e represents an accurate measurement of the intrinsic rate constant k₁ for electron transfer. However, as the applied potential is less than E°, the reversibility of the electron-transfer process becomes increasingly more important, and the rate constants for reverse electron transfer k_-t and decomposition k₂ of the electrogenerated intermediate have to be taken into account.     

Trapping of Tricarbonyl(η1,η2‐homoallyl)iron and Tricarbonyl(η3‐allyl)iron Anion Intermediates with 2‐(Phenylsulfonyl)‐3‐phenyloxaziridine

The addition of reactive carbanions to (η⁴‐1,3‐diene)Fe(CO)₃ complexes at ?78 °C and 25 °C produced putative homoallyl and allyl anion complexes, respectively. Reaction of the reactive intermediates with 2‐(phenylsulfonyl)‐3‐phenyloxaziridine afforded nucleophilic substituted (η⁴‐1,3‐diene)Fe(CO)₃ complexes.     

Tricarbonyl(dialkylamidocyclohexa-1,3-diene)iron: Preparation,Isomerization and Stereochemistry

The direct reaction of iron pentacarbonyl with diethylamidocyclohexadiene gave three isomeric tricarbonyliron complexes, 1, 2 and 3. Only 1 isomerized to give 2 under acidic conditions, whereas 3 remained unchanged. The chemical properties of the tricarbonyl(amidocyclohexadiene)iron complexes differed from those of the tricarbonyl(carboxycyclohexadiene)iron complexes. Complex 3 which underwent no hydride abstraction with triphenylmethyl hexafluorophosphate, has an exo stereochemistry.     

Kinetic Regularities Governing the Reaction of Electrodeposition of Iron from Solutions of Citrate Complexes of Iron(III)

The kinetics of a multistep reaction of electrodeposition of iron out of aqueous citrate-containing solutions of trivalent iron is investigated. It is shown that concentrations of major solution components affect the partial current density of discharge of ions of divalent iron. It is established that the deposition of metallic iron occurs as a result of discharge of intermediates, which are hydroxy complexes of divalent iron. Kinetic parameters and mechanism of the reaction of discharge of complexes [FeOH]⁺ to a metallic state are determined. It is mentioned that the formation of poorly soluble hydroxy compounds of trivalent iron in a near-electrode layer leads to a decrease in the iron deposition current.     

Investigation of the Amide Linkages on Cooperative Supramolecular Polymerization of Organoplatinum(II) Complexes

Cooperative supramolecular polymerization of π-conjugated compounds into one-dimensional nanostructures has received tremendous attentions in recent years. It is commonly achieved by incorporating amide linkages into the monomeric structures, which provide hydrogen bonds for intermolecular non-covalent complexation. Herein, the effect of amide linkages is elaborately studied, by comparing supramolecular polymerization behaviors of two structurally similar monomers with the same platinum(II) acetylide cores. As compared to the N-phenyl benzamide linkages, N-[(1S)-1-phenylethyl] benzamide linkages give rise to effective chirality transfer behaviors due to the closer distances between the chiral units and the platinum(II) acetylide core. They also provide stronger intermolecular hydrogen bonding strength, which consequently brings higher thermo-stability and enhanced gelation capability for the resulting supramolecular polymers. Supramolecular polymerization is further strengthened by varying the monomers from monotopic to ditopic structures. Hence, with the judicious modulation of structural parameters, the current study opens up new avenues for the rational design of supramolecular polymeric systems.     

Remote Tricarbonyl(diene)iron Substituent Effect on Ester Heterolysis. The Solvolyses of 5,6,7,8-Tetramethylidenebicyclo[2.2.2]oct-2-yl Methanesulfonate and of its Tricarbonyliron Mono- and Dinuclear Complexes

Buffered acetolyses and hydrolyses of 5,6,7,8-tetramethylidenbicyclo[2.2.2]oct-2-yl methanesulfonate ( 17 ), of its ‘syn-endo’ ( 18 ), ‘syn-exo’ ( 19 ), ‘anti-endo’ ( 20 ), ‘anti-exo’ ( 21 ) tricarbonyliron complexes and of its ‘anti-exo,syn-endo’ ( 22 ) and ‘anti-endo,syn-exo’ ( 23 ) bis(tricarbonyliron) dinuclear complexes have been investigated (product analysis and kinetics). In contract with the solvolyses of the uncomplexed mesylate 17 , the solvolyses of the complexed esters can be highly chemo- and stereoselective. The nature of the products (non-rearranged bicyclo[2.2.2]oct-2yl vs. rearranged bicyclo[3.2.1]oct-2-yl derivatives) depends on the relative configuration of the tricarbonyl(diene)iron moieties and on the medium. The rates of solvolyses of 17 are only slightly affected by complexation of one or both s-cis-butadiene units with Fe(CO)₃ groups, except in the cases where the diene moiety ‘anti’ with respect to the mesylate is complexed onto its ‘endo’ face ( 20,23 ). In these cases, significant rate-retardation effects are observed, consistent with the inductive effect of the Fe(CO)₃ substituent. Such retardation effects are overwhelmed by competing accelerating homoallylic participation by uncoordinated ‘anti’ -diene moieties ( 18,19 ) or, as in the case of the ‘anti-exo’-Fe(CO)₃ complexes 21 and 22 , by possible direct metal participation to the ionization process.     

(NH_4)_(42)[Mo_(132)O_(372)(CH_3COO)_(30)(H_2O)_(72)]膜修饰电极的构筑和电化学性质的研究

由于过渡金属替代的多金属氧酸盐(polyoxometalates)的催化、磁性、电化学等性质,越来越受到人们的关注~([1-7]). 目前世界上约有10亿人生活在缺碘地区,碘的缺乏严重影响人类健康.对食物、生物临床、环境及工业中碘含量检测很有实际意义.     

Oxidation of Tricarbonyl (η1 η2-but-3-en-1-yl)iron(0)and Tricarbonyl (η3-allyl)iron(0) Anion Complexes with Dioxygen

The addition of reactive carbanions to tricarbonyl(η⁴-1,3-diene)iron(0) complexes proceeded at ?78 °C to give putative tricarbonyl(η¹,η²-but-3-en-1-y1)iron(0) anion complexes and at 25 °C to produce postulated tricarbonyl(η³-allyl)iron(O) anion complexes; trapping of reactive intermediates with dioxygen produced γ,δ-unsaturated acids and allylic alcohols, respectively.     

Bifunctional (Cyclopentadienone)Iron–Tricarbonyl Complexes: Synthesis,Computational Studies and Application in Reductive Amination

Reductive amination under hydrogen pressure is a valuable process in organic chemistry to access amine derivatives from aldehydes or ketones. Knölker’s complex has been shown to be an efficient iron catalyst in this reaction. To determine the influence of the substituents on the cyclopentadienone ancillary ligand, a series of modified Knölker’s complexes was synthesised and fully characterised. These complexes were also transformed into their analogous acetonitrile iron–dicarbonyl complexes. Catalytic activities of these complexes were evaluated and compared in a model reaction. The scope of this reaction is also reported. For mechanistic insights, deuterium‐labelling experiments and DFT calculations were undertaken and are also presented.     

Mechanical Modulation of the Solid-State Luminescence of Tricarbonyl Rhenium(I) Complexes through the Interplay between Two Triplet Excited States

Mechanoresponsive luminescence (MRL) materials promise smart devices for sensing, optoelectronics and security. We present here the first report on the MRL activity of two Re^I complexes, opening up new opportunities for applications in these fields. Both complexes exhibit marked solid-state luminescence enhancement (SLE). Furthermore, the pristine microcrystalline powders emit in the yellow-green region, and grinding led to an amorphous phase with concomitant emission redshift and shrinking of the photoluminescence (PL) quantum yields and lifetimes. Quantum chemical calculations revealed the existence of two low-lying triplet excited states with very similar energy levels, that is, ³IL and ³MLCT, having, respectively, almost pure intraligand (IL) and metal-to-ligand charge-transfer (MLCT) character. Transition between these states could be promoted by rotation around the pyridyltriazole−phenylbenzoxazole bond. In the microcrystals, in which rotations are hindered, the ³IL state induces the prominent PL emission at short wavelengths. Upon grinding, rotation is facilitated and the transition to the ³MLCT state results in a larger proportion of long-wavelength PL. FTIR and variable-temperature PL spectroscopy showed that the opening of the vibrational modes favours non-radiative deactivation of the triplet states in the amorphous phase. In solution, PL only arises from the ³MLCT state. The same mechanism accounts for the spectroscopic differences observed when passing from crystals to amorphous powders, and then to solutions, thereby clarifying the link between SLE and MRL for these complexes.     

Square Planar Platinum(II) Complexes with N,S-Donor Ligands: Synthesis,Characterisation, DNA Interaction and Cytotoxic Activity

The platinum(II) complexes with N,S-donor ligand have been synthesised and characterised by physiological techniques like elemental, electronic, Fourier transform infrared, hydrogen-1 nuclear magnetic resonance (¹H NMR) and liquid chromatography–mass spectrometry spectra. The synthesised complexes have been checked for their DNA binding ability by absorption titration and viscosity measurement, and the results show that the complexes binds to herring sperm DNA (HS DNA) via covalent mode of binding. The DNA cleavage activity of synthesised complexes has been carried out by gel electrophoresis experiment using supercoiled form of pUC19 DNA, showing the unwinding of the negatively charged supercoiled DNA. Brine shrimp (Artemia cysts) lethality bioassay technique has been applied for the determination of toxic property of synthesised complexes in terms of micromolars.     

Influence of the trans Substituent on N2 Bonding in Iron(ii)–Phosphane Complexes: Structure,Synthesis, and Properties of the Monomeric Adducts trans-[FeXN2(depe)2]BPh4, X=Cl,Br

Not a dimer but a monomer was found in the X-ray structure analysis of the complex “trans-[{FeCl(depe)₂}₂(µ-N₂)](BPh₄)₂” (depe=Et₂PCH₂CH₂PEt₂). The complexes [FeXN₂(depe)₂]BPh₄ (X=Cl, Br; structure of the cation for X=Cl shown on the right) are much less stable than the analogous hydride compounds and undergo N₂ exchange at room temperature even in the solid state.     

Investigation of the Metal Cation Binding Properties of Macrocyclic EDTA–Bis(Amide) Complexes by Potentiometry and Stopped-Flow Spectrophotometry

The protonation constants of macrocyclic EDTA–bis(amide), EDTA–EAM (1), EDTA–PAM (2), EDTA–BAM (3), and EDTA–PenAM (4), and the stability constants of theirLn³⁺and Cu²⁺complexes have been determined by potentiometric titration at 25.0 ± 0.1°C andI= 0.10M(KCl). The dissociation rates of someLn³⁺complexes have been measured by stopped-flow and conventional spectrophotometry at 25.0 ± 0.1°C andI= 0.10M(NaClO₄). The first protonation constants of the ligands were lower than that of EDTA, reflecting the strong electron-withdrawing ability of the carbonyl group. The stability constants and dissociation rates ofLn³⁺complexes followed the orderLn(1)⁺〈Ln(2)⁺〉Ln(3)⁺〉Ln(4)⁺. An increase in ring size from 13 (2) to 15 (4) by addition of the carbon chain between two amide nitrogens of the ligands leads to an increase in the thermodynamic and kinetic stability of the complexes. However,1shows a different behavior in the complexes because of its greater rigidity and basicity.     

Interaction between N,N,N′,N′-tetramethylthiuram disulfide and cobalt(II) salts: Dependence of the product composition and structure on the nature of the anion

The reaction between CoX₂ (X = Br, I, NCS, NO₃) and N,N,N′,N′-tetramethylthiuram disulfide is found to be a redox process. Irrespective of the anion, it yields cobalt(III) dimethyldithiocarbamate {Co(Me₂Dtc)₃}. The other products vary in number and composition: Me₄Ditt[CoBr₄] forms for X = Br; Me₂Tmi[I₃], S, and Co(Me₂Dtc)₃ · I₂, for X = I; [Co(Me₂Ditc)₄](NCS)₂, for X = NCS; CoSO₄ · 7H₂O and NO, for X = NO₃ (Me₄Ditt = 3,6-di(dimethyliminio)-1,2,4,5-tetrathian, Me₂Tmi = dimethylthioxomethylideneimonium, and Me₂Ditc = dimethyldithiocarbamatoisothiocyanate). The compounds have been characterized by chemical analysis, X-ray diffraction, mass spectrometry, conductivity measurements, IR and electronic spectroscopy, and magnetic measurements. The structure of Co(Me₂Dtc)₃ · I₂ was determined by X-ray crystallography.     

(Cyclopentadienone)iron Complexes: Synthesis,Mechanism and Applications in Organic Synthesis

(Cyclopentadienone)iron tricarbonyl complexes are catalytically active, inexpensive, easily accessible and air-stable that are extensively studied as an active pre-catalyst in homogeneous catalysis. Its versatile catalytic activity arises exclusively due to the presence of a non-innocent ligand, which can trigger its unique redox properties effectively. These complexes have been employed widely in (transfer)hydrogenation (e. g., reduction of polar multiple bonds, Oppenauer-type oxidation of alcohols), C−C and C−N bond formation (e. g., reductive aminations, α-alkylation of ketones) and other synthetic transformations. In this review, we discuss the remarkable advancement of its various synthetic applications along with synthesis and mechanistic studies, until February 2021.