Mechanism of Pd(OAc)2/Pyridine Catalyst Reoxidation by O2: Influence of Labile Monodentate Ligands and Identification of a Biomimetic Mechanism for O2 Activation

Aerobic oxidation : Mechanisms of aerobic oxidation of the Pd^II(OAc)₂/pyridine catalyst system were evaluated by using density functional theory methods. The results reveal that labile monodentate ligands, such as pyridine, favor a catalyst reoxidation pathway that proceeds via Pd⁰, rather than direct reaction of O₂ with a Pd^II–hydride intermediate (see scheme).

     

Theoretical study on AlnO2 (n = 1–10) clusters and O2 adsorption on the Al(111) surface

The structural properties of neutral and ionic Al_nO₂ (n = 1–10) clusters have been systematically investigated using the density functional method B3LYP with a standard 6‐311+G(d) basis set. The calculated results show that in the Al_nO, Al_nO₂, and Al_nO (n ≥ 3) clusters, O atoms tend to penetrate into the aluminum clusters with some Al atoms moving outward. The binding energies and natural charges populations indicate that the oxygen‐etching is generally stronger in the order Al < Al_n < Al for n < 3, and Al > Al_n > Al for n ≥ 3. To further understand the mechanism of interaction between Al and O₂, the adsorption of O₂ on the Al(111) surface was studied using the density functional theory with plane wave pseudopotential method. The calculated results are consistent with the experimental observation that the O₂ molecule would dissociate on the Al(111) surface and be adsorbed in adjacent hollow sites, forming a local structure of Al₃O–Al₃O. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Synthesis of Orthorhombic Mo‐V‐Sb Oxide Species by Assembly of Pentagonal Mo6O21 Polyoxometalate Building Blocks

Mix and match : The pentagonal [Mo₆O₂₁]^n? polyoxomolybdate building block assembles with other sources of Mo, V, and Sb ions to form an orthorhombic Mo‐V‐Sb oxide. The first single‐crystal X‐ray analysis of an orthorhombic Mo–V‐based oxide, a promising catalyst for light alkane selective oxidation known as the “M1 phase”, revealed the structure of the compound.

     

Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)4S6], [(RSn)3S4]2−, [(RT)2(CuPPh3)6S6], and [(RSn)6(OMe)6Cu2S6]4− (R=C2H4COOH,CMe2CH2COMe; T=Ge,Sn)

Caged chalcogens : A series of novel, functionalized T_nS_m cages (T=Ge, Sn; n/m=4:6, 3:4) with terminal COO(H) or COMe groups were synthesized and show further reactivity toward Cu^I complexes (an example of which is shown here) and to hydrazines. This led to the generation of functionalized Cu/T/S clusters or the formation of Schiff bases at the C?O groups, respectively, with or without further fragmentation of the T/S core.

     

Theoretical study of one‐electron bonds in a series of high‐spin lithium–beryllium–hydrogen clusters: “Valence shell single‐electron repulsion” rule and electron localization function analysis

A series of high‐spin clusters containing Li, H, and Be in which the valence shell molecular orbitals (MOs) are occupied by a single electron has been characterized using ab initio and density functional theory (DFT) calculations. A first type (⁵Li₂, ⁿ⁺¹LiH_n+ (n = 2–5), ⁸Li₂H) possesses only one electron pair in the lowest MO, with bond energies of ～3 kcal/mol. In a second type, all the MOs are singly occupied, which results in highly excited species that nevertheless constitute a marked minimum on their potential energy surface (PES). Thus, it is possible to design a larger panel of structures (⁸LiBe, ⁷Li₂, ⁸Li, ⁴LiH⁺, ⁶BeH, ⁿ⁺³LiH (n = 3, 4), ⁿ⁺²LiH (n = 4–6), ⁸Li₂H, ⁹Li₂H, ²²Li₃Be₃ and ²²Li₆H), single‐electron equivalent to doublet “classical” molecules ranging from CO to C₆H₆. The geometrical structure is studied in relation to the valence shell single‐electron repulsion (VSEPR) theory and the electron localization function (ELF) is analyzed, revealing a striking similarity with the corresponding structure having paired electrons. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Probing the ultrafast photoelectron spectra of Br2 molecule

The time‐dependent‐wave‐packet method is applied to study the ionization of Br₂ molecule with four ionization processes. The ground state absorption makes the photoelectron to be left in the three final ionic states: Br (X²∑), Br (A²∏_u), and Br (B²∑), and each population of these ionic states is related with the laser intensities. The information of the dissociation can be got by analyzing the photoelectron features of the transient wave packet, which also suggests that an ionization process occurs during the dissociation, and the Br atoms that mainly resulted from the dissociation of Br₂ (C¹∏_u) are ionized at later time delays as the dissociation is nearly complete. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

An efficient and modified biginelli one‐pot synthesis of new isoxazole substitted 3,4‐dihydropyrimidin‐2(1H)‐ones and thiones catalyzed by VCl3

An efficient and modified Biginelli one‐pot synthesis of new‐isoxazole substituted 3,4‐dihydropyrimidin‐2(1H)‐ones and thiones from aromatic aldehydes, ketoamide and urea/thiourea in acetonitrile using VCl₃ as the catalyst is described.     

Ti0.99Pd0.01O2−δ: A New Pt‐free Catalyst for High Rates of H2+O2 Recombination with High CO Tolerant Capacity

A platinum‐free H ₂ /O ₂ recombination catalyst , Ti_0.99Pd_0.01O_2?δ, is synthesized by a solution combustion method where Pd²⁺ ions adsorb protonic H₂^δ+ ion and oxygen on the oxide ion vacancy sites (see picture). The rate of H₂+O₂ recombination at 50 °C is 15 μmoles g^?1 s^?1, which is much higher than that of Pt‐containing catalysts.

     

Density functional theory study of geometry and stability of small Zrn (n = 2–10) clusters

Geometric structures, electronic properties, and stabilities of small Zr_n and Zr (n = 2–10) clusters have been investigated using density functional theory with effective core potential LanL2DZ basis set. For both neutral and charged systems, several isomers and different multiplicities were studied to determine the lowest energy structures. Many most stable states with high symmetry were found for small Zr_n clusters. The most stable structures and symmetries of Zr clusters are the same as the neutral ones except n = 4 and 7. We found that the clusters with n > 3 possess highly compact structures. The clusters are inclined to form the caged‐liked geometry containing pentagonal structures for n > 8, which is in favor of energy. From the formation energy and second‐order energy difference, we obtained that 2‐, 5‐, 7‐atoms of neutral and 4‐, 7‐atoms cationic clusters are the magic numbers. Furthermore, the highest occupied molecular orbital‐lowest unoccupied molecular orbital gaps display that the Zr₃, Zr₆, Zr, and Zr are more stable in chemical stability. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Synthesis of Stereoblock Elastomeric Poly(propylene)s Using a (2‐PhInd)2ZrCl2 Metallocene Catalyst in the Presence of Co‐Catalyst Mixtures: Study of Activity and Molecular Weight

The effect of adding various aluminum alkyls (R = Et, i‐Bu) on the polymerization of propylene is studied using a (2‐PhInd)₂ZrCl₂ pre‐catalyst. A mild deactivating effect is found upon addition of TIBA, whereas TEA shows a sharp deactivating effect. Increasing amounts of AlR₃ results in a significant activity increase for TIBA, but an activity plateau for TEA. AlR₃ imposes remarkably different effects on the molecular weight and stereochemical microstructure of polymers. As the TIBA concentration increases, $\overline {M} _{{\rm v}} $ increases at first, growing from 49 000 to 72 000, but subsequently drops to 40 000. For TEA, $\overline {M} _{{\rm v}} $ decreases sharply, plummeting from 49 000 to 17 000. Both TIBA and TEA increase the mmmm pentad content from 7.9 to 23.5% and 17.6%, respectively.

     

Methodical Thermolysis of [Ba2Ti2(thd)4(OnPr)8(nPrOH)2] under Autogenous Pressure Followed by Combustion for the Synthesis of Dielectric Tetragonal BaTiO3 Nanopowder

Tetragonal powders : Dielectric tetragonal BaTiO₃ nanopowder was synthesized in a solvent‐less, efficient process by the thermolysis of a single [Ba₂Ti₂(thd)₄(OnPr)₈(nPrOH)₂] precursor in a closed reactor at 700 °C under autogenous pressure, followed by combustion. The BaTiO₃ nanopowder is characterized thoroughly, employing advanced morphological, compositional, structural, and thermal techniques, and the dielectric constant is accounted.

     

Investigation of Catalytic Chain Transfer Copolymerization of Methacrylates

Batch experiments were carried out to investigate the kinetics of catalytic chain transfer copolymerization of methyl methacrylate and n‐butyl methacrylate. The Predici® model developed to represent the system describes the numerous experimental data measured at high concentrations of Co(II ) catalyst, taking into account the chain‐length dependencies of termination, propagation and catalytic chain transfer. The constants for catalytic chain transfer are determined as 2.3 × 10⁴ for both methyl methacrylate and n‐butyl methacrylate from fitting the experimental data. Two inhibition mechanisms are shown to describe the decrease of the polymerization rate in the presence of catalyst equally well, with an unknown impurity dissolved in initiator introduced to explain experimental profiles measured at high initiator concentrations.

     

Synthesis and Characterization of Homopolymers and Copolymers Containing closo‐[B12H12]2− Boron Cage Derivatives

Chains of cages : Neutral/ionic [B₁₂H₁₂]^2? boron‐cage‐functionalized methacrylate and styrene homopolymers or copolymers (see picture) are non‐crystalline solids, T_g increases as the number of B₁₂ cages in the chain of polystyrene increases, and homopolymers retain more weight than the copolymers when heated to 400 °C.

     

Selective Isomerization of Epoxides to Allylic Alcohols Catalyzed by TiO2‐Supported Gold Nanoparticles

ReacTiO ₂ ns for rings : Gold nanoparticles supported on TiO₂ are used as a novel heterogeneous catalyst for the isomerization of epoxides to allylic alcohols by a concerted mechanism (see scheme). The reaction proceeds in high yields and the product selectivity is often remarkable.

     

On the 4JHH long‐range coupling in 2‐bromocyclohexanone: conformational insights

2‐Bromocyclohexanone is a model compound in which a ⁴J_{H2, H6} coupling constant is observed, whereas the corresponding ⁴J_{H2, H4} is absent. The observed long‐range coupling is not only a result of the known W‐type coupling, in the axial conformation, but also because of the less usual diaxial spin–spin coupling in the equatorial conformer. The carbonyl group plays a determining role in describing the coupling pathway, as concluded by natural bond orbital (NBO) analysis; although the and interactions in the axial conformer contribute for transmitting the spin information associated with the W‐type coupling, the strong and hyperconjugations in the equatorial conformer define an enhanced coupling pathway for ⁴J_{H2, H6}, despite the inhibition of this coupling because of interaction and the large carbonyl angle. These findings provide the experimental evidence that orbital interactions contribute for the conformational isomerism of 2‐bromocyclohexanone. Copyright © 2008 John Wiley & Sons, Ltd.     

How an Inert‐Gas Matrix Can Modify the Molecular Properties of Lanthanide Trifluoride

Ab initio computations performed on LaF₃?Ar_n (n=1–21) complexes allow a quantification of the short‐range many‐body interactions arising in the argon matrix. It is shown that the molecular properties of LaF₃ are strongly influenced by the embedding medium. The largest investigated cluster, LaF₃?Ar₂₁, resembles an hcp structure with the LaF₃ molecule occupying the central substitutional site (see figure).

     

Extraction of Uranium from Aqueous Solutions by Using Ionic Liquid and Supercritical Carbon Dioxide in Conjunction

Super powers! Uranium(VI) ions can be extracted from aqueous solutions into supercritical CO₂ (sc‐CO₂) via an ionic liquid phase that contained tri‐n‐butyl phosphate (TBP) as a complexing agent (see figure). This process has potential applications in the nuclear industry for removing actinides from nuclear waste.

     

The Role of the Support in the Performance of Grafted Metallocene Catalysts

A series of supports – differing in their textural properties, the nature of their surface sites, and in their crystallinities – were investigated in the sequential grafting reaction of Cp₂ZrCl₂ and (nBuCp)₂ZrCl₂ mixtures. The catalyst systems were analyzed by Rutherford backscattering spectrometry, AFM, EXAFS, and nitrogen adsorption. All systems were shown to be active in ethylene polymerization reactions when methylaluminoxane was used as the cocatalyst. Experimental results are discussed in terms of the relationships between the grafted metal content, the catalyst activity, the surface roughness and polarity, the interatomic Zr–C and Zr–O distances of the grafted species and the molecular weights of the resulting polyethylenes.

     

Enhancement of H2 Adsorption in Coordination Framework Materials by Use of Ligand Curvature

Curvy ligands for H ₂ storage? Enhancement of H₂ adsorption has been observed in coordination framework materials, an example of which is depicted, by the introduction of phenanthrene and 9,10‐dihydrophenanthrene groups into porous Cu^II–carboxylate framework materials of NbO topology.

     

Cation–Cation Interactions,Magnetic Communication,and Reactivity of the Pentavalent Uranium Ion [U(NtBu)2]+

Communication is important : The dimeric bis(imido) uranium complex [{U(NtBu)₂(I)(tBu₂bpy)}₂] (see picture; U green, N blue, I red) has cation–cation interactions between [U(NR)₂]⁺ ions. This f¹–f¹ system also displays f orbital communication between uranium(V) centers at low temperatures, and can be oxidized to generate uranium(VI) bis(imido) complexes.