Transmetalation in the Suzuki–Miyaura Coupling: The Fork in the Trail

The Suzuki–Miyaura coupling is one of the few transition‐metal‐catalyzed C? C bond‐forming reactions that have been used in applications ranging from discovery chemistry to manufacturing processes. Although coupling proceeds through the generic three‐stage ‘oxidative addition, transmetalation, reductive elimination’ sequence, there are a number of features that differentiate the Suzuki–Miyaura process from other transition‐metal‐catalyzed cross‐couplings. Most of these features are centered around, or are a consequence of, activation of the boron reagent for transmetalation through one or both of two distinct pathways. This review focuses on the evidence that has been presented for this ‘fork in the trail′, and the potential to apply such mechanistic insight to the design of reaction conditions.     

Phase Stability and Elastic Properties of Chromium Borides with Various Stoichiometries

Phase stability is important to the application of materials. By first‐principles calculations, we establish the phase stability of chromium borides with various stoichiometries. Moreover, the phases of CrB₃ and CrB₄ have been predicted by using a newly developed particle swarm optimization (PSO) algorithm. Formation enthalpy–pressure diagrams reveal that the MoB‐type structure is more energetically favorable than the TiI‐type structure for CrB. For CrB₂, the WB₂‐type structure is preferred at zero pressure. The predicted new phase of CrB₃ belongs to the hexagonal P‐6m2 space group and it transforms into an orthorhombic phase as the pressure exceeds 93 GPa. The predicted CrB₄ (space group: Pnnm) phase is more energetically favorable than the previously proposed Immm structure. The mechanical and thermodynamic stabilities of predicted CrB₃ and CrB₄ are verified by the calculated elastic constants and formation enthalpies. The full phonon dispersion calculations confirm the dynamic stability of WB₂‐type CrB₂ and predicted CrB₃. The large shear moduli, large Young’s moduli, low Poisson ratios, and low bulk and shear modulus ratios of CrB₄? PS_C and CrB₄? PS_D indicate that they are potential hard materials. Analyses of Debye temperature, electronic localization function, and electronic structure provide further understanding of the chemical and physical properties of these borides.     

硼的添加对Ti0.26Zr0.07V0.24Mn0.1Ni0.33贮氢合金结构和电化学性能的影响

Ti0.26Zr0.07V0.24Mn0.1Ni0.33Bx(x=0~0.10)系列合金均有V基固溶体相和C14型Laves相两相组成。添加B可提高Ti0.26Zr0.07V0.24Mn0.1Ni0.33合金的放电容量,Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.1合金电极在60 mA·g-1电流放电时的放电容量达到476.7 mAh·g-1。B的添加不同程度地降低了合金的高倍率放电性能,使合金电极表面上电化学反应的电荷转移电阻(R ct)显著增加,交换电流密度(I0)显著降低。添加B可显著改善Ti0.26Zr0.07V0.24Mn0.1Ni0.33合金电极的高温放电性能,Ti0.26Zr0.07V0.24Mn0.1Ni0.33B0.025合金电极在343 K高温下其放电容量达到525.6 mAh·g-1。     

碳化硅和碳化硼在电催化中的应用

燃料电池是具有广泛应用前景的新能源技术。碳载铂基催化剂（Pt/C）是最常用的燃料电池电极催化剂,不过Pt/C稳定性较差、且成本高昂,严重限制了燃料电池的规模化应用。共价型碳化物碳化硅和碳化硼,由于具有极强的共价键,其物化稳定性优异,成为制备高稳定性、低成本的燃料电池催化剂的重要基础材料。本文总结了相关研究成果,介绍了碳化硅和碳化硼的独特优势,讨论了相关研究的发展方向。     

Gas storage of simple molecules in boron oxide nanocapsules

The capability of the B₂₀O₃₀ nanocapsule to store H₂, N₂, CO, CO₂, NH₃, CH₄, and Cl₂ molecules on the outer surface and inside of the cage was investigated using Monte Carlo simulations, long‐range and dispersion corrected density functional theory, and Møller–Plesset second‐order perturbation theory. Also, Monte Carlo simulations were employed to investigate the adsorption behavior of larger number of guest molecules inserted into and onto the larger B₈₀O₁₂₀ and B₂₀O₃₀@B₈₀O₁₂₀ cages. Absolute localized molecular orbitals energy decomposition analysis was used to describe the nature of intermolecular interactions in these endohedral and exohedral complexes. It is found that the hydrogen and ammonia gases are diffused to the inside of spherical B₂₀O₃₀ capsule, while other guest molecules prefer to interact with the outer surface of spherical and pyramidal capsules. For B₈₀O₁₂₀, up to 26 H₂ and 11–14 N₂, CO, CO₂, NH₃, and CH₄ molecules are stored inside the capsule. The residual molecules are adsorbed on the outer surface of nanocapsule. © 2013 Wiley Periodicals, Inc.     

Anodic stripping voltammetry of antimony at unmodified carbon electrodes

Antimony is an element of significant environmental concern, yet has been neglected relative to other heavy metals in electroanalysis. As such very little research has been reported on the electroanalytical determination of antimony at unmodified carbon electrodes. In this paper we report the electrochemical determination of Sb(III) in HCl solutions using unmodified carbon substrates, with focus on non-classical carbon materials namely edge plane pyrolytic graphite (EPPG), boron doped diamond (BDD) and screen-printed electrodes (SPE). Using differential pulse anodic stripping voltammetry, EPPG was found to give a considerably greater response towards antimony than other unmodified carbon electrodes, allowing highly linear ranges in nanomolar concentrations and a detection limit of 3.9?nM in 0.25?M HCl. Furthermore, the sensitivity of the response from EPPG was 100 times greater than for glassy carbon (GC). Unmodified GC gave a comparable response to previous results using the bare substrate, and BDD gave an improved, yet still very high limit of detection of 320?nM compared to previous analysis using an iridium oxide modified BDD electrode. SPEs gave a very poor response to antimony, even at high concentrations, observing no linearity from standard additions, as well as a major interference from the ink intrinsic to the working electrode carbon material. Owing to its superior performance relative to other carbon electrodes, the EPPG electrode was subjected to further analytical testing with antimony. The response of the electrode for a 40?nM concentration of Sb(III) was reproducible with a mean peak current of 1.07?µA and variation of 8.4% (n?=?8). The effect of metals copper, bismuth and arsenic were investigated at the electrode, as they are common interferences for stripping analysis of antimony.     

Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid‐State NMR Spectroscopies and DFT Calculations

Boronic acids (R‐B(OH)₂) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R‐B(OH)₃^?) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C₄H₉‐B(OH)₃]₂, which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid‐state NMR spectroscopy (¹H, ¹³C, ¹¹B and ⁴³Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave—GIPAW—method). These data allow relationships between the geometry around the OH groups in boronates and the IR and ¹H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic–inorganic materials containing boronate building blocks.     

Borylated Arylisoquinolines: Photophysical Properties and Switching Behavior of Promising Tunable Fluorophores

A series of nine borylated arylisoquinolines has been prepared with systematic variation in their electronic properties and their photophysical properties were investigated. The color of their fluorescence can be finely tuned by changing the properties of the aryl moiety, which is involved in internal‐charge‐transfer processes. For example, methoxy‐substituted compound 5 showed an intense green emission, whereas dimethylamino‐substituted compound 6 showed an orange‐red emission. These new fluorophores were tested for their potential as molecular switches with external ionic stimuli, such as protons and fluoride ions. On the one hand, protonation of the isoquinoline moiety led to fluorescence enhancement for compounds that showed weak charge transfer and fluorescence quenching for compounds that showed strong charge transfer. On the other hand, the formation of ate complexes with fluoride led to strong fluorescence quenching in all of the investigated cases.     

Synthesis,Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes

Plumbacyclopentadienylidenes, in which the lead atoms have divalent states and are coordinated by THF, pyridine and N‐heterocyclic carbene, were synthesized and characterized. The THF‐ and pyridine‐stabilized compounds can be regarded as rare examples of hypervalent 10‐X‐4 species. The equilibrium between the THF adduct and the free plumbacyclopentadienylidene was evidenced by spectroscopic analysis and theoretical calculations. The THF adduct in benzene converted into a plumbylene dimer, where one of the lead centers is coordinated by THF and the other lead atom is coordinated by a divalent lead atom, the dimer gradually decomposing into spiroplumbole. The THF adduct unexpectedly reacted with trifluoroborane and trichlorogallane to afford fluoroborole and chlorogallole, which are the first examples of non‐annulated fluoroborole and gallole, respectively.