Proposal of a New Hf(IV)/Zr(IV) Separation System by the Solvent Extraction Method

A liquid-liquid extraction study has been conducted to separate hafnium from zirconium, using Cyanex 301 in kerosene. Noticeably, it is the first time that Cyanex 301 is utilized to separate Hf(IV) from Zr(IV). In this series of experiments, several parameters influencing the separation have been investigated, such as the initial pH, the extractant concentration, the metal ion concentration, the temperature, the type of the diluents and the salt addition. Regarding the aging of the Zr(IV) and Hf(IV) solutions, the solutions with a maximum 3 d aging time could be used with no difficulties. It was observed that the initial pH increase caused an increase in the Zr(IV)/Hf(IV) separation factor. Moreover, the distribution decreased with the temperature increase, suggesting that the reaction is exothermic. In agreement with the resulting data, the optimum separation factor illustrates the value of 7 at a pH of 4.00 in the presence of NaCl as an added salt. The attractive characteristics of the presently designed method are the use of low acidic nitrate solutions, the lack of using thiocyanate and a higher extractability of hafnium-Cyanex 301 relative to zirconium-Cyanex 301 complexes.     

Group IV M‐POSS (M=Zr,Hf) Coordination Polymers

The synthesis and characterization of Zr‐POSS and Hf‐POSS coordination polymers were reported. The IR data and the solid‐state ²⁹Si MAS NMR indicated the existence of Si? O? M linkage. The polarized optical microscopy images and the XRD data suggested their crystalline nature.     

Zirconium(IV) catalysis in perborate oxidation of iodide

Zirconium(IV) catalyzes perborate oxidation of iodide ion. In acidic solution the oxidation is zero order with respect to perborate, first order with respect to Zr(IV), independent of [H⁺] and exhibits Michaelis-Menten dependence on [I⁻]. Mechanistic pathway of the catalysis is discussed and a rate equation is derived.     

Facing unexpected reactivity paths with Zr(IV)-pyridylamido polymerization catalysts

This work provides original insights to the better understanding of the complex structure-activity relationship of Zr(IV)-pyridylamido-based olefin polymerization catalysts and highlights the importance of the metal-precursor choice (Zr(NMe(2))(4) vs. Zr(Bn)(4)) to prepare precatalysts of unambiguous identity. A temperature-controlled and reversible σ-bond metathesis/protonolysis reaction is found to take place on the Zr(IV)-amido complexes in the 298-383 K temperature range, changing the metal coordination sphere dramatically (from a five-coordinated tris-amido species stabilized by bidentate monoanionic {N,N(-)} ligands to a six-coordinated bis-amido-mono-amino complexes featured by tridentate dianionic {N(-),N,C(-)} ligands). Well-defined neutral Zr(IV)-pyridylamido complexes have been prepared from Zr(Bn)(4) as metal source. Their cationic derivatives [Zr(IV) N(-),N,C(-)}Bn](+)[B(C(6)F(5))(4)](-) have been successfully applied to the room-temperature polymerization of 1-hexene with productivities up to one order of magnitude higher than those reported for the related Hf(IV) state-of-the-art systems. Most importantly, a linear increase of the poly(1-hexene) M(n) values (30-250 kg mol(-1)) has been observed upon catalyst aging. According to that, the major active species (responsible for the increased M(n) polymer values) in the aged catalyst solution, has been identified.     

Homogeneous and heterogeneous catalysis: bridging the gap through surface organometallic chemistry

Surface organometallic chemistry is an area of heterogeneous catalysis which has recently emerged as a result of a comparative analysis of homogeneous and heterogeneous catalysis. The chemical industry has often favored heterogeneous catalysis, but the development of better catalysts has been hindered by the presence of numerous kinds of active sites and also by the low concentration of active sites. These factors have precluded a rational improvement of these systems, hence the empirical nature of heterogeneous catalysis. Catalysis is primarily a molecular phenomenon, and it must involve well-defined surface organometallic intermediates and/or transition states. Thus, one must be able to construct a well-defined active site, test its catalytic performance, and assess a structure-activity relationship, which will be used, in turn-as in homogeneous catalysis-to design better catalysts.By the transfer of the concepts and tools of molecular organometallic chemistry to surfaces, surface organometallic chemistry can generate well-defined surface species by understanding the reaction of organometallic complexes with the support, which can be considered as a rigid ligand. This new approach to heterogeneous catalysis can bring molecular insight to the design of new catalysts and even allow the discovery of new reactions (Ziegler-Natta depolymerization and alkane metathesis). After more than a century of existence, heterogeneous catalysis can still be improved and will play a crucial role in solving current problems. It offers an answer to economical and environmental problems faced by industry in the production of molecules (agrochemicals, petrochemicals, pharmaceuticals, polymers, basic chemicals).     

Homogeneous catalysis: Kinetics and mechanism of oxidation of Ru(II) sensitizers by inorganic peroxides

The present research work involves the nature of interaction between the Ru(II) complex and inorganic peroxides in the absence of excitation by light photons. We synthesized a photosensitizer, ([Ru(dcbpy)₂(biq)]Cl₂·3H₂O) and studied its thermal degradation in the presence of inorganic peroxides (hydrogen peroxide, peroxomonosulfate and peroxodisulfate). Progress of the thermal reaction between the Ru(II) complex and each peroxide in 0.5 M H⁺ solutions was followed spectrophotometrically by monitoring the disappearance of the Ru(II) complex at its maximum absorbance (λ = 514 nm). The reactivities of the peroxides were compared and suitable mechanisms proposed.     

Spectroelectrochemical Properties and Catalytic Activity in Cyclohexane Oxidation of the Hybrid Zr/Hf-Phthalocyaninate-Capped Nickel(II) and Iron(II) tris-Pyridineoximates and Their Precursors

The in situ spectroelectrochemical cyclic voltammetric studies of the antimony-monocapped nickel(II) and iron(II) tris-pyridineoximates with a labile triethylantimony cross-linking group and Zr(IV)/Hf(IV) phthalocyaninate complexes were performed in order to understand the nature of the redox events in the molecules of heterodinuclear zirconium(IV) and hafnium(IV) phthalocyaninate-capped derivatives. Electronic structures of their 1e-oxidized and 1e-electron-reduced forms were experimentally studied by electron paramagnetic resonance (EPR) spectroscopy and UV−vis−near-IR spectroelectrochemical experiments and supported by density functional theory (DFT) calculations. The investigated hybrid molecular systems that combine a transition metal (pseudo)clathrochelate and a Zr/Hf-phthalocyaninate moiety exhibit quite rich redox activity both in the cathodic and in the anodic region. These binuclear compounds and their precursors were tested as potential catalysts in oxidation reactions of cyclohexane and the results are discussed.     

Electronic and Steric Effects on L-Lactide Ring-Opening Polymerization with NSSN-type Zr(IV) Complexes

In this work the mechanism of L-lactide polymerization promoted by NSSN zirconium complexes was investigated through DFT methods with the aim to understand as the electronic and steric features of the ligand affect the energy reaction. It was observed that the rate determining step of the process is the opening of the L-lactide ring and that by increasing the steric hindrance, evaluated by changing geometric parameters and topographic steric maps, or the electron-withdrawing properties of the ligand, the corresponding energy barrier increases. On the other hand, calculations foresee that a small and electron-releasing substituent on the nitrogen atom of the ligand, such as the methyl group, is desirable in order to obtain NSSN zirconium based catalysts with improved activity in the ROP of the L-lactide.     

Bis-β-(diketonates) Zn(II) complexes substituted with thiophene: Electropolymerization,homogeneous and heterogeneous catalysis for ring opening polymerization of lactide

Two Bis-β-diketonate zinc (II) complexes were synthesized using 1-(thiophen-2-yl)butane-1,3-dione and 1-(thiophen-2-yl)-3-(thiophen-3-yl)propane-1,3-dione as ligands. By electropolymerization of their thiophenyl groups, the metallopolymers deposited on FTO electrodes were obtained. The main objective was to study the reactivity of these compounds as ROP catalysts for PLA synthesis, using directly the zinc complexes (homogeneous catalysis) and also the modified electrodes with metallopolymers (heterogeneous catalysis). The homogeneous catalysis studies allowed the optimization of the polymerization conditions, such as reaction time, catalyst concentration, and the use of benzyl alcohol as cocatalyst, as well as their influence on the conversion rate, average molecular weight and polydispersity of PLA, using rac-LA and L-LA as monomers. Also, the effect on tacticity and thermal properties were discussed. Finally, the ROP studies using immersed modified electrodes in the polymerization medium were carried out under optimized experimental conditions. These tests were positive for one of the studied compounds, reaching conversions of up to 67%. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 557–567     

The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]

The binary zirconium and hafnium polyazides [PPh₄]₂[M(N₃)₆] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF₄ by fluoride–azide exchange reactions with Me₃SiN₃ in the presence of two equivalents of [PPh₄][N₃]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N₃)₄], [M(N₃)₅]^? and [M(N₃)₆]^2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.     

Comparison of homogeneous and heterogeneous Ga(III) catalysis in the cycloisomerization of 1,6-enynes

We describe a study of the gallium(III)-catalyzed 1,6-enynes cycloisomerization reaction in both homogeneous and heterogeneous conditions. With GaBr₃ in homogeneous conditions, some particularities were observed in terms of selectivity compared to reported GaCl₃-catalyzed reactions. The transfer of the reaction in heterogeneous conditions was realized by supporting Ga(III) salts onto montmorillonite. Both systems were compared based on reaction times, conversion, and selectivity and showed complementary activities.     

Dititanium-containing 19-tungstodiarsenate(III) [Ti2(OH)2As2W19O67(H2O)]8-: synthesis, structure, electrochemistry, and oxidation catalysis

The dititanium-containing 19-tungstodiarsenate(III) [Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)](8-) (1) has been synthesized and characterized by IR, TGA, elemental analysis, electrochemistry, and catalytic studies. Single-crystal X-ray analysis was carried out on Cs(8)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)].2CsCl.12H(2)O (Cs-1), which crystallizes in the monoclinic system, space group P2(1)/m, with a=12.7764(19), b=19.425(3), c=18.149(3) A, beta=110.234(3) degrees, and Z=2. Polyanion 1 comprises two (B-alpha-As(III)W(9)O(33)) Keggin moieties linked through an octahedral {WO(5)(H(2)O)} fragment and two unprecedented square-pyramidal {TiO(4)(OH)} groups, leading to a sandwich-type structure with nominal C(2v) symmetry. Synthesis of 1 was accomplished by reaction of TiOSO(4) and K(14)[As(2)W(19)O(67)(H(2)O)] in a 2:1 molar ratio in aqueous, acidic medium (pH 2). Polyanion 1 could also be isolated as a tetra-n-butyl ammonium (TBA) salt, {(n-C(4)H(9))(4)N}(5)H(3)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)] (TBA-1). TBA-1 was studied by cyclic voltammetry in acetonitrile (MeCN) solutions containing 0.1 M LiClO(4) and compared with the results obtained with Cs-1 in aqueous media. In MeCN, the Ti(IV) and W(VI) waves could not be separated distinctly. An important adsorption phenomenon on the glassy carbon working electrode was encountered both in cyclic voltammetry and in controlled potential electrolysis and was confirmed by Electrochemical Quartz Crystal Microbalance (EQCM) studies on a carbon film. TBA-1, dissolved in MeCN, reacts with H(2)O(2) to give peroxo complexes stable enough for characterization by UV-visible spectroscopy, cyclic voltammetry, and EQCM. TBA-1 shows high catalytic activity (TOF=11.3 h(-1)) in cyclohexene oxidation with aqueous H(2)O(2) producing products typical of a heterolytic oxidation mechanism. The stability of TBA-1 under turnover conditions was confirmed by using IR, UV-visible spectroscopy as well as cyclic voltammetry.     

First-Principles Calculations of Phonons and Thermodynamic Properties of Zr(Hf)S2-Based Nanotubes

Comparative hybrid density functional calculations on the structure, stability, and phonon frequencies of monolayers and single-walled nanotubes are performed for Zr(Hf)S₂ disulfides. The first-principles calculations of HfS₂-based nanotubes are made for the first time. The symmetry analysis of infrared and Raman active vibrational modes in ZrS₂ and HfS₂ nanotubes is made using the induced representations of the isogonal point groups of line groups. It is shown that the number of infrared and Raman active modes is constant for NTs with the same chirality type. The correlation of the phonon modes of the nanotubes of relatively large diameters with those of monolayer is analyzed. The thermodynamic functions of monolayers and nanotubes with various chirality and diameters are calculated on the basis of the obtained phonon frequencies. It is established that the phonon contribution to the nanotube strain energy is small, but may be important for an accurate estimate of the stability of the nanotubes of small diameters. The calculated results show that the thermal contributions to Helmholtz free energy are positive; thereby they slightly reduce the stability of ZrS₂ and HfS₂ nanotubes at elevated temperatures. © 2019 Wiley Periodicals, Inc.     

ChemInform Abstract: Cs2Cu3MIVF12 (MIV : Zr,Hf) - Crystal Structure and Magnetic Behavior.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Pyrolysis of metallocene complexes (ηC5H4R)2MR: An organometallic route to metal carbide (MC) materials (M = Ti,Zr, Hf)

The following compounds were prepared and their pyrolysis in a stream of argon was studied: (η⁵-C₅H₅)₂Ti(C?CC₆H₅)₂, (η⁵-C₅H₄SiMe₃)₂-Ti(SH)₂, [(η⁵-C₅H₅)Ti(μ-CH₂)]₂, (η⁵-C₅H₅)₂ZrR₂-(R?CH₂, CH₂C₆H₅, N(CH₃)₂), (η⁵-C₅H₄CH₃)₂-Zr(C?CC₆H₅)₂, [(η⁵-C₅H₄SiMe₃)₂Zr(μ-S)]₂, [(η⁵-C₅H₄SiMe₃)₂Hf(μ-S)]₂ and (η⁵-C₅H₄SiMe₃)₂Hf-(C?CC₆H₅)₂. The products of bulk pyrolysis of these materials were formed in 20–40% yield, based on the charged sample weight, and consisted mainly of titanium carbide together with small amounts of amorphous carbon.     

ChemInform Abstract: Studies on the Electronic Structure of MCl4 (M: Ti,Zr, Hf) Type Molecules by the MS-Xα Method.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Ni- and Pd-based homogeneous catalyst systems for direct oxygenation of C(sp3)-H groups

Developing catalytic approaches to selective activation and functionalization of C–H bonds in hydrocarbons and complex organic molecules has been considered as a challenging goal. Recently, significant efforts have been aimed at the search for efficient nickel- and palladium-based catalyst systems, capable of conducting direct aliphatic C–H oxygenation with high and predictable chemoselectivity and regioselectivity. The present review focuses on the advances in homogeneous oxidation of hydrocarbon C(sp³)–H groups, catalyzed by nickel and palladium complexes, and covers the publications of the past 15 years. Correlations between the structure of the metal-based catalyst, steric and electronic properties of the ligands, catalytic conditions, and the catalytic reactivity (efficiency, chemoselectivity, and regioselectivity) are discussed.