ESR spectra of γ-irradiated samples of iron(iii) binuclear complexes

-Irradiation of -oxo-bridged binuclear iron complexes Fe^III ₂OL _n in a glycerol or dimethylformamide matrix at 77 K affords unstable mixed-valence Fe^IIF^III forms resulting from the transfer of a mobile electron generated by the ionizing radiation. These nonequilibrium forms retain the ligand environment of the original complexes, and their ESR spectra at 77–200 K are characterized by an asymmetric signal with an axially anisotropicg-factor, which is in agreement with the spectra of the Fe^IIFe syu forms obtained by chemical reduction.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 869–871, April, 1996.     

Voltammetric and titrimetric study of acid-base properties of some μ-oxo dimeric iron(III) complexes inDMF

Summary The acid-base properties of the -oxo bridged dimeric iron complexes [FeL]₂O with the ligands based on S-alkyl-1,4-bis(substituted salicylidene)isothiosemicarbazide and a tetramer with S-methyl-1,4-bis(salicylidene)isothiosemicarbazide, {[FeL]₂O}₂I₃·I₂, were investigated by cyclic voltammetry at glassy carbon electrode inDMF. Studies were carried out in the presence of either a weak (phenol) or a strong (HClO₄ aq.) acid. The stoichimoetry of the reaction, changes in the general voltammetric pattern and the electrode reaction mechanism were discussed. These studies served as the basis for three-electrode amperometric titrations to determine the content of several of these complexes.

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Voltammetrische und titrimetrische Untersuchung der Säure-Base-Eigenschaften einiger -oxo dimerer Eisen(III)-Komplexe inDMF-Lösungen

Zusammenfassung Die Säure-Base-Eigenschaften einiger dimerer -oxo-Eisen(III)-Komplexe [FeL]₂O mit Liganden auf Basis von 1,4-bis(substituierten Salicyliden)S-(alkyl)isothiosemicarbaziden sowie eines tetrameren Komplexes mit 1,4-Bis(salicyliden)S-methylisothiosemicarbazid, {[FeL]₂O}₂I₃·I₂, wurden mittels zyklischer Voltammetrie an der Glaskohlenstoffelektrode inDMF-Lösungen untersucht. Die Messungen wurden in Gegenwart entweder einer schwachen (Phenol) oder einer starken (HClO₄ aq.) Säure ausgeführt. Die Stöchiometrie der Reaktion, die Änderungen der voltammetrischen Kurven und der Elektroden-Reaktionsmechanismus wurden diskutiert. Diese Untersuchungen stellten eine Basis für Drei-Elektroden amperometrische Titrationen dar, die für die Bestimmung des Gehalts einiger dieser Komplexe angewendet wurden.

     

Formation of nitridotechnetium (VI) μ-oxo dimer complexes with EDTA and EDDA

Reactions of [⁹⁹TcNCl₄]^– with ethylenediaminetetraacetic acid (EDTA) and ethylenediamine-N, N-diacetic acid (EDDA) in a mixture of water and acetone gave Tc^VIN-EDTA and Tc^VIN-EDDA complexes. The infrared spectra of both reaction products showed the existence of the TcN and C=O groups. The elemental analysis indicated the 11 TcN-ligand ratio in the EDTA and EDDA complexes. Electrophoresis showed that the Tc^VI-EDTA complex was an anionic species in a perchlorate solution. For the Tc^VIN-EDDA complex, neutral and anionic species were formed, depending on the pH of the solution. Formation of the -oxo dimer complexes was suggested from the UV-Vis absorption spectra.     

Synthesis and magnetic interaction of μ-2-chloroterephthalato binuclear iron (Ⅱ) complexes

Four μ-2-chloroterephthalato binuclear iron(Ⅱ) complexes, namely [Fe2 (CTPHA) L4]-(ClO4)2, where L stands for 4,4'-dimethyl-2,2'-bipyridine (Me2-bpy); 2,9-dimethyl-l, 10-phenanthro-line (Me2-phen); 5-chloro-l, 10-phenanthroline (Cl-phen); 4, 7-diphenyl-l, 10-phenanthroline (Ph2-phen), respectively, and CTPHA represents 2-chlorolerephthalate dianion, have been synthesized and characterized. Based on the elemental analyses, molar conductance measurements and spectroscopic studies, extended CTPHA-bridged structures consisting of two iron(Ⅱ) ions, each in a distorted octahedral environment, are proposed for these complexes. [Fe2 CTPHA)-(Me2-bpy)4] (ClO2 (1) and [Fe2(CT-PHA)·(Me2-phen)4](ClO4)2 (2) complexes were characterized by variable temperature magnetic susceptibility (4-300 K) measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 · S2 , giving the exchange integrals J = - 1.28 cm-1 for 1 and J = - 1.85 cm-1 for 2. These r     

ESR study of μ-allyl Co(II) complexes in Ziegler type catalytic systems

ESR study of the interaction between the components of the catalytic system Co(acac)₂- PBu₃-LiBu in the presence of butadiene revealed the formation of stable paramagnetic cobalt complexes containing a PBu₃ ligand and butadiene molecules. Complexes (³-R)₂CoPBu₃ (where R is allyl, crotyl, benzyl) have been synthesized by ordinary methodsin situ, in order to identify the structures of the complexes. ESR parameters and geometry of the central core have been determined. The influence of the nature of phosphine ligands on the parameters of the ESR spectra has been studied. The general regularities in the ESR spectra of (³-R)2CoPBu₃ and the complexes formed in the catalytic system have been revealed.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 152–155, January, 1994.     

Chemistry of iron complexes—VI. ESR,spectroscopic and other studies of complexes of iron(III) perchlorate and isothiocyanate with bis(tertiary phosphine/arsine oxides)

A series of complexes of bis(tertiary phosphine/arsine oxides), Ph₂E(O) (CH₂)_nE(O)Ph₂ with iron(III) perchlorate and isothiocyanate, viz. [Fe(mdpo)₃] (ClO₄)₃·H₂O, [Fe(edpo)₂ (H₂O)₂] (ClO₄)₃, [Fe(hdpo)₂ (H₂O)₂] (ClO₄)₃, [Fe(edao) (O₂ClO₂)] (ClO₄)₂·H₂O, [Fe(bdao) (OClO₃)₂] (ClO₄)·H₂O, [Fe(bdpo) (ac)₂ (OClO₃)] (ClO₄)₂, [Fe(mdpo)₂ (NCS)₂] (NCS)·3H₂O, [Fe(bdpo) (NCS)₃]·H₂O], [Fe(L — L) (NCS)₃] (L — L) = edpo, edao, bdao and hdpo) [(L — L, n, E; mdpo, 1, P; edpo (or edao), 2, P (or As); bdpo (or bdao), 4, P (or As) and hdpo, 6, P], has been studied with the help of i.r., far i.r. and u.v.-vis, ESR spectra, magnetic moments, X-ray diffraction, TGA and conductance data. All the complexes are high-spin. Possible structures are suggested.     

Oxidation-promoted synthesis of ferrocenyl planar chiral rhodium(iii) complexes for C–H functionalization catalysis

The chemical oxidation of rhodium(i) complexes [Rh(L)(COD)][BF4], where L is a ferrocenyl phosphine/N-heterocyclic carbene ligand, with 2 equiv. of a triaryl-aminium salt [(4-BrC6H4)3N][BF4] in acetonitrile gave planar chiral, air-stable [Rh(L–H)(MeCN)3][BF4]2 complexes where the ferrocene (C5H4CH2ImR or C5H4CH2BImCH2Mes) ring has been C–H activated at the position 2 in good to excellent yields. An important reactivity difference between our complexes and the ubiquitous [Cp*Rh(MeCN)3]X2 complex has been observed in the Grignard-type arylation of 4-nitrobenzaldehyde.     

Binuclear cationic μ-bromo complexes of vanadium(II)

The compounds [V₂(μ-Br)₃L₆]BPh₄, with L = 3-methyltetrahydrofuran (1) and tetrahydrofuran (2), have been prepared. The crystal and molecular structures of 1 have been determined. The compound crystallizes in space group Cc with unit cell dimensions a = 18.499(3), b = 10.923(3), c = 29.619(7) Å, β = 103.18(2)^o, V = 5827(5) ų and Z = 4. The [V₂(μ-Br)₃(CH₃C₄H₇O)₆]⁺ ion is analogous to the [V₂(μ-Cl)₃L₆]⁺ cations previously described, but has a longer V—V distance, viz. 3.146(4) A. The UV-vis spectrum shows a double spin-flip transition but it is extremely weak compared to that in the chloro analog. Qualitatively, this was expected because of the ca 0.16 Å increase in the V—V distance, but the magnitude of the decrease (∼ 5 fold) is of interest.     

Bis(imino)pyridine–iron(II) complexes for ethylene polymerization

Ethylene polymerization was carried out using new late transition metal 2,6-bis(imino)pyridine catalysts containing different substituents (H, NO₂, and OCH₃) at the para position of the pyridine ring, activated by methylaluminoxane. Effects of polymerization parameters such as ethylene pressure, reaction temperature, hydrogen concentration and structure variation on the catalysts activities and polymer properties were investigated. Introducing the functionality in the para-position of the pyridine ring of the catalysts had remarkable effect on the polymer properties as well as the catalysts activities.     

The structure of μ-oxo dimer of aluminium(III) porphyrin: a theoretical study

The gas-phase molecular structure of μ-oxo dimer of aluminium(III) porphyrin, (AlP)₂O, has been studied for the first time by density functional theory calculations using the B3LYP and M06 functionals and triple-ζ valence basis sets. The molecule has two conformers with equilibrium structures of D _4d and D _4h symmetries with parallel macrocycles and aluminium-oxygen distances of 1.680–1.684 Å (M06/cc-pVTZ). The aluminium atom lies out of the plane of the four central nitrogen atoms and forms a square-based pyramid with them, with the following parameters (M06/cc-pVTZ): r(Al–N) = 2.030–2.031 Å, r(N···N) = 2.803–2.804 Å (the side of the pyramid base), z(Al)–z(N) = 0.434–0.446 Å (the height of the pyramid).     

Crystal structure of a μ-oxo-bridged dimeric iron(III) complex

A dimeric [{Fe(5-ClL1)}₂(μ-O)], [H₂-5-ClL1 = N,N′-bis(5-chloro-2-hydroxybenzylidene)-2-methylpropane-1,2-diamine] tetradentate Schiff-base complex, 1, has been synthesized and its crystal structure has been determined by single crystal X-ray diffraction analysis. Structural analysis of complex 1 shows that the complex is a centrosymmetric dimer. Each of the Fe(III) ions has a five-coordinate geometry and one oxygen atom bridges two Fe(III) ions to form a μ-oxo structure. The geometry around iron atom can be described as a square based pyramid with the FeN₂O₂ coordination plane and oxo ligand.     

Synthesis and characterization of binuclear μ-oxo and μ-telluro molybdenum(V) complexes, [CpMo(O)(μ-Te)]2

Pyrolysis of an in-situ generated intermediate, produced in the reaction of [Cp^∗MoCl₄], 1, (Cp^∗ = η⁵-C₅Me₅) with [LiBH₄·THF], with an excess of difuryl ditelluride in toluene at 90 °C yielded syn and anti isomers of [Cp^∗Mo(O)(μ-Te)]₂ (2, 3) and [Cp^∗₂Mo₂O₂(μ-O)(μ-Te)] (4, 5). In a similar fashion, dibenzyl diselenide yielded syn and anti isomers of [Cp^∗Mo(O)(μ-Se)]₂ (6, 7), along with the known nido-[(Cp^∗Mo)₂B₄H₈Se₂]. Note that in parallel with 2-7, [(Cp^∗Mo)₂B₅H₉] was isolated as the major product in both cases. Compounds 2-7 have been isolated in modest yield as orange to brown crystalline solids. All the new compounds have been characterized in solution by mass, IR, ¹H, ¹³C, ⁷⁷Se and ¹²⁵Te NMR spectroscopy, and the structural types were unequivocally established by crystallographic analysis of 2-4 and 7.     

Sorption of iron(III)–alginate complexes on cellulose fibres

Multivalent ions take a significant role in the sorption of soluble polysaccharides on solid cellulose substrates and thus demonstrate an important principle in structural polysaccharide organisation. Sorption of Fe(III)–alginate complexes on lyocell fibres as model for the insoluble cellulose matrix has been studied between pH 3–13, at 30 and 60 °C. Sorption maximum of the Fe(III)–alginate complex was observed at pH 3 where the sorbed amounts of alginate and iron were 6,600 and 85 mg iron per kg cellulose respectively. Under the experimental conditions used, a concentration of 0.05 mM Fe(III) is sufficient to achieve surface sorption of Fe(III)–alginate complex. The alginate sorption exhibited minor dependence on molar ratio of Fe(III) to alginate. In environmental scanning electron microscopy no deposition of Fe-hydroxides on the fiber surface was detected. The thickness of the adsorbed Fe(III)–alginate layer on the fiber surface was estimated with 12–22 nm. Tensile strength and abrasion resistance of Fe(III)–alginate treated fibers were not reduced through the sorption treatment. Alginate modified cellulose is of interest as material for medical application, as sorbent and textile finish.     

Nucleotide hydrolysis in the presence of μ-hydroxo-bridged-cobalt(III) complexes

Abstract

Two cobalt(III) complexes with tridentate ligands, the acyclic diethylenetriamine and macrocyclic 1,4,7-triazacyclononane, were examined as potential catalysts for the hydrolysis of adenosine 5′-triphosphate (ATP). Studies were performed primarily at pH 4.5, where the two complexes were in the binuclear di-μ-hydroxo forms. For both complexes, a rapid initial hydrolysis with first order dependence on the concentration of ATP was observed, k_obs of approximately 0.20 min^?1, followed by very slow hydrolysis. Deuterium isotope studies done in D₂O showed a normal isotope effect with k_H/k_D = 1.8. Spectral investigations and ⁵⁹Co NMR studies indicated that the biphasic nature of the hydrolysis reaction may be due to the formation of a complex in which inorganic phosphate is coordinated to the cobalt, effectively poisoning the catalyst.     

Synthesis and structure of tetranuclear copper(Ⅱ) complex containing μ4-oxo bridge

A new dinucleating Schiff base ligand HL(L=C13H17N2O3) has been synthesised and characterized.The single crystal structure of its complex [L2Cu4O(AcO4)]·2H2O has beendetermined by X-ray diffraction methods.The result indicates that every Cu atom has its square pyramidal coordination polyhedron and there is a tetrahedral Cu4O core in the complex molecule.Its active sites where catalytic oxidation of dioxygen occurs have been inferred.     

Synthesis and magnetism of μ-isophthalato dinuclear lanthanide(Ⅲ) complexes

Seven new μ-isophthalato dinuclear lanthanide(Ⅲ) complexes, namely [Ln2(IPHTA)(Me2-phen)4-(ClO4)2](ClO4)2 (Ln = La, Nd, Sm, Eu, Gd, Ho, Er), where Me2-phen denotes 2,9-dimethyl-1, 10-phenanthroline (Me2-phen) , IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [Gd2( IPHTA) (Mez-phen)4 (ClO4)2] (ClO4)2 complex were measured in the temperature range of 4-300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 · S2, giving the exchange parameter J =- 0.19 cm-1 . This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(Ⅲ)-Gd(Ⅲ) ions within the complex.     

Chemistry of iron complexes—II. Spectroscopic,magnetic and other studies of new complexes of iron(III) with bis(tertiary phosphine/arsine oxides)

Spectroscopic (i.r., far i.r., ESR, u.v.-vis) magnetic, TGA, molar conductance and X-ray diffraction studies of new complexes of iron(III) halides with bis(tertiary phosphine/arsine oxides) Ph₂E(O)(CH₂)_nE(O)Ph₂(LL) have been reported. The complexes are of the types: (a) [Fe(LL)₂Cl] [FeCl₄]₂ (n = 2,4; E = As) and (b) [Fe(LL)₂Br₂] [FeBr₄] [E, n:P (1,2,4,6); As(2,4)]. The cations [Fe(LL)₂Br₂]⁺ were assigned a trans octahedral structure. The far i.r. data support chloro-bridged octahedral structures for the cations [Fe(LL)₂Cl]²⁺.     

Reactivity of Cr(III) μ-oxo compounds: catalyst regeneration and atom transfer processes

Oxidation of CpCr[(XylNCMe)(2)CH] (Xyl = 2,6-Me(2)C(6)H(3)) with pyridine N-oxide or air generated the μ-oxo dimer, {CpCr[(XylNCMe)(2)CH]}(2)(μ-O). The μ-oxo dimer was converted to paramagnetic Cr(III) CpCr[(XylNCMe)(2)CH](X) complexes (X = OH, O(2)CPh, Cl, OTs) via protonolysis reactions. The related Cr(III) alkoxide complexes (X = OCMe(3), OCMe(2)Ph) were prepared by salt metathesis and characterized by single crystal X-ray diffraction. The interconversion of the Cr(III) complexes and their reduction back to Cr(II) with Mn powder were monitored using UV-vis spectroscopy. The related CpCr[(DepNCMe)(2)CH] (Dep = 2,6-Et(2)C(6)H(3)) Cr(II) complex was studied for catalytic oxygen atom transfer reactions with PPh(3) using O(2) or air. Both Cr(II) complexes reacted with pyridine N-oxide and γ-terpinene to give the corresponding Cr(III) hydroxide complexes. When CpCr[(DepNCMe)(2)CH] was treated with pyridine N-oxide in benzene in the absence of hydrogen atom donors, a dimeric Cr(III) hydroxide product was isolated and structurally characterized, apparently resulting from intramolecular hydrogen atom abstraction of a secondary benzylic ligand C-H bond followed by intermolecular C-C bond formation. The use of very bulky hexaisopropylterphenyl ligand substituents did not preclude the formation of the analogous μ-oxo dimer, which was characterized by X-ray diffraction. Attempts to develop a chromium-catalyzed intermolecular hydrogen atom transfer process based on these reactions were unsuccessful. The protonolysis and reduction reactions of the μ-oxo dimer were used to improve the previously reported Cr-catalyzed radical cyclization of a bromoacetal.     

Catalytic oxidation of aliphatic alcohols in the tetraaquapalladium(ii) complex—iron(iii)—dioxygen system

The selective low-temperature (40—70 °C) catalytic oxidation of methanol, propan-1-ol, and propan-2-ol in the presence of the tetraaquapalladium(ii) complex and iron(iii) ions and/or molecular oxygen as cooxidants was studied. The corresponding carbonyl compound is the product of alcohol oxidation. The kinetic regularities of the reaction were established. In the reaction mechanism proposed, the key step is palladium(i) formation.     

Mössbauer and electronic spectral studies of iron(III) complexes of oximes

The hydroxo-bridge complexes of the type [Fe(2)(ligand-H)(4)(OH)(2)] with bidentate nitrogen-oxygen donor ligands, viz. 2-hydroxynaphthaldehydeoxime [hnoH(2)], 2-hydroxyacetphenoneoxime [haoH(2)], salicylaldooxime [SalH(2)], 2-hydroxypropiophenoneoxime [hnoH(2)] have been prepared. All the complexes have been characterized by elemental analysis, magnetic moments, electronic and M?ssbauer spectral studies. M?ssbauer parameters of the complexes clearly suggest high spin configuration of Fe(III) showing lower magnetic moment to that of the spin only value, i.e. 5.92 BM. It may be due to the antiferromagnetic interaction between Fe(III) centers.