Pressure-induced novel structure with graphene-like boron-layer in titanium monoboride

The recent discovery of the novel boron-framework in boron-rich metal borides with complex structures and intriguing features under high pressure has stimulated the search into the unique boron-network in the metal monoborides or boron-deficient metal borides at high pressure. Herein, based on the particle swarm optimization algorithm combined with first-principles calculations, we thoroughly explored the structural evolution and properties of TiB up to 200 GPa. This material undergoes a pressure-induced phase transition of $Pnma$ $\to $ $Cmcm$ $\to $ $Pmmm$. Besides of two known phases $Pnma$ and $Cmcm$, an unexpected orthorhombic $Pmmm$ structure was predicted to be energetically favored in the pressure range of 110.88-200 GPa. Intriguingly, the B covalent network eventually evolved from a one-dimensional zigzag chain in $Pnma$-TiB and $Cmcm$-TiB to a graphene-like B-sheet in $Pmmm$-TiB. On the basis of the microscopic hardness model, the calculated hardness ($H_{\rm v}$) values of $Pnma$ at 1 atm, $Cmcm$ at 100 GPa, and $Pmmm$ at 140 GPa are 36.81 GPa, 25.17 GPa, and 15.36 GPa, respectively. Remarkably, analyses of the density of states, electron localization function and the crystal orbital Hamilton population (COHP) exhibit that the bonding nature in the three TiB structures can be considered as a combination of the B-B and Ti-B covalent interactions. Moreover, the high hardness and excellent mechanical properties of the three TiB polymorphs can be ascribed to the strong B-B and Ti-B covalent bonds.     

Bipolar Electrochemistry Exfoliation of Layered Metal Chalcogenides Sb2S3 and Bi2S3 and their Hydrogen Evolution Applications

Efficient exfoliation and downsizing of Sb₂S₃ and Bi₂S₃ layered compounds by using scalable bipolar electrochemistry on their suspensions in aqueous media are here demonstrated. The resulting samples were characterized in detail by transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy; their electrochemistry toward hydrogen evolution was also investigated. Hydrogen evolution ability of exfoliated Sb₂S₃ and Bi₂S₃ was investigated and compared to the bulk counterparts.     

Electrophilicity Scale of Activated Amides: 17O NMR and 15N NMR Chemical Shifts of Acyclic Twisted Amides in N−C(O) Cross-Coupling

The structure and properties of amides are of tremendous interest in organic synthesis and biochemistry. Traditional amides are planar and the carbonyl group non-electrophilic due to n_N→π*_C=O conjugation. In this study, we report electrophilicity scale by exploiting ¹⁷O NMR and ¹⁵N NMR chemical shifts of acyclic twisted and destabilized acyclic amides that have recently received major attention as precursors in N-C(O) cross-coupling by selective oxidative addition as well as precursors in electrophilic activation of N-C(O) bonds. Most crucially, we demonstrate that acyclic twisted amides feature electrophilicity of the carbonyl group that ranges between that of acid anhydrides and acid chlorides. Furthermore, a wide range of electrophilic amides is possible with gradually varying carbonyl electrophilicity by steric and electronic tuning of amide bond properties. Overall, the study quantifies for the first time that steric and electronic destabilization of the amide bond in common acyclic amides renders the amide bond as electrophilic as acid anhydrides and chlorides. These findings should have major implications on the fundamental properties of amide bonds.     

Sterically Constrained Bicyclic Phosphines: A Class of Fascinating Compounds Suitable for Application in Small Molecule Activation and Coordination Chemistry

Bicyclic phosphines with two annulated, electronically unsaturated five-membered heterocycles are available through facile routes. In most cases, their phosphorus atoms are bound to heteroatoms such as oxygen or nitrogen (PN₃ or PN₂O), whereas homoleptic coordination by three sp²-hybridized carbon atoms has been reported only recently. Steric strain causes unique reactivity. Oxidative addition of halogens, N−H or O−H bonds have afforded phosphoranes as valuable materials for secondary processes. Ring opening was identified as an important step for the understanding of these reactions and has been observed experimentally with a diphosphorus-based ring system. A PH₂ derivative has been considered as a model system for small molecule activation, and hydrogen transfer to a diazo compound was observed experimentally. Several of these phosphines are excellent ligands for the coordination of transition-metal atoms. The very bulky PC₃ compound has a basicity similar to that of PPh₃ and may allow the synthesis of complexes with unusually low coordination numbers at the metal atoms. These phosphines found recently renewed interest as promising reagents in various secondary transformations such as the activation of σ-bonds or in coordination chemistry.     

Two‐Dimensional Haeckelite NbS2: A Diamagnetic High‐Mobility Semiconductor with Nb4+ Ions

In all known Group 5 transition‐metal dichalcogenide monolayers (MLs), the metal centers carry a spin, and their ground‐state phases are either metallic or semiconducting with indirect band gaps. Here, on grounds of first‐principles calculations, we report that the Haeckelite polytypes 1 S ‐NbX₂ (X=S, Se, Te) are diamagnetic direct‐band‐gap semiconductors even though the Nb atoms are in the 4+ oxidation state. In contrast, 1 S ‐VX₂ MLs are antiferromagnetically coupled indirect‐band‐gap semiconductors. The 1 S phases are thermodynamically and dynamically stable but of slightly higher energy than their 1 H and 1 T ML counterparts. 1 S ‐NbX₂ MLs are excellent candidates for optoelectronic applications owing to their small band gaps (between 0.5 and 1 eV). Moreover, 1 S ‐NbS₂ shows a particularly high hole mobility of 2.68×10³ cm² V⁻¹ s⁻¹, which is significantly higher than that of MoS₂ and comparable to that of WSe₂.     

Transition-Metal Free Catalytic Synthesis of Trifluoromethyl Indolines by [4+1] Cycloaddition of Trifluoromethyl Benzoxazinones with Sulfur Ylides

Stereoselective catalytic synthesis of 3-trifluoromethyl indolines through the [4+1] cycloaddition of benzoxazinones and sulfur ylides in a transition-metal-free manner was developed. In the presence of a catalytic amount of sodium hydride, aza-ortho-quinone methide intermediates were formed from trifluoromethyl benzoxazinones through decarboxylation after the first nucleophilic attack of sulfur ylides, which progressed to a second nucleophilic attack of sulfur ylides, resulting in the [4+1] cycloaddition. The key for this catalytic transformation is the dual attack of sulfur ylides on substrates. This unique transition-metal-free protocol is applicable to the synthesis of non-fluorinated vinyl-, ethynyl- or methyl-substituted indolines. The synthesis of 3-trifluoromethyl indoles was also achieved described under stoichiometric conditions.     

过渡金属-配体σ键键能在碳-氢键活化中的应用

过渡金属催化的碳-氢(C-H)键活化因其优异的原子经济性及步骤简便性在过去几十年间蓬勃发展,已成为当前构建复杂化合物最常用的策略之一.对该过程中活性中间体的热力学研究有助于加深人们对反应机理的理解,指导新催化剂、新反应的理性设计.然而,近年来该领域的发展颇为缓慢,相应的报道十分零散,缺少系统的归纳和总结.本综述简要梳理了过渡金属-配体σ键键能的研究历程,并举例阐述了这些热力学参数在分析反应可行性、判断反应选择性等方面的应用,旨在推动过渡金属络合物相关的热力学研究的快速发展.     

一种饱和Keggin硅钨酸盐过渡金属衍生物[Cu(biim)_2]_4[α-SiW_(12)O_(40)]_2·4H_2O（英文）

在水热环境下,将Na10[α-SiW9O34]爛18H2O和CuCl2爛2H2O在2,2′-联咪唑和4,4′-联吡啶存在下反应合成一种饱和Keggin硅钨酸盐杂化物[Cu(biim)2]4[α-SiW12O40]2爛4H2O(1),并通过红外光谱,X射线光电子能谱和X射线单晶衍射进行了结构表征.化合物1分子包含2个中性的Keggin[Cu(biim)2]2[α-SiW12O40]单元和4个结晶水分子.值得注意的是在[α-SiW12O40]4-单元中,与硅原子相连的每个氧原子无序排列在两个位置,这导致了硅原子呈现立方体的几何构型.中性Keggin型[Cu(biim)2]2[α-SiW12O40]单元具有中心对称性,两个[Cu(biim)2]2+配离子对称连接在[α-SiW12O40]4-的两端.邻近的[Cu(biim)2]2[α-SiW12O40]单元之间通过氢键作用形成三维的超分子结构.