A Cationic Zinc Hydride Cluster Stabilized by an N‐Heterocyclic Carbene: Synthesis,Reactivity, and Hydrosilylation Catalysis

The trinuclear cationic zinc hydride cluster [(IMes)₃Zn₃H₄(THF)](BPh₄)₂ ( 1 ) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH₂]₂ with a Brønsted acid or by addition of the putative zinc dication [(IMes)Zn(THF)]²⁺. A triply bridged thiophenolato complex 2 was formed upon oxidation of 1 with PhS? SPh. Protonolysis of 1 by methanol or water gave the corresponding trinuclear dicationic derivatives. At ambient temperature, 1 catalyzed the hydrosilylation of aldehydes, ketones, and nitriles. Carbon dioxide was also hydrosilylated under forcing conditions when using (EtO)₃SiH, giving silylformate as the main product.     

Enantioselective Synthesis of Functionalized Arenes by Nickel-Catalyzed Site-Selective Hydroarylation of 1,3-Dienes with Aryl Boronates

A catalytic method for the site-selective and enantioselective synthesis of functionalized arenes by the intermolecular hydroarylation of terminal and internal 1,3-dienes with aryl pinacolato boronates is reported. The reactions are promoted by 5.0 mol % of a readily available monodentate phosphoramidite-Ni complex in ethanol, affording a variety of enantioenriched products in up to 96 % yield and 99:1 er. Mechanistic studies indicate that Ni–allyl formation is irreversible and related to the nature of the arylboronate.     

Homogeneous Oligomeric Ligands Prepared via Radical Polymerization that Recognize and Neutralize a Target Peptide

Abiotic ligands that bind to specific biomolecules have attracted attention as substitutes for biomolecular ligands, such as antibodies and aptamers. Radical polymerization enables the production of robust polymeric ligands from inexpensive functional monomers. However, little has been reported about the production of monodispersed polymeric ligands. Herein, we present homogeneous ligands prepared via radical polymerization that recognize epitope sequences on a target peptide and neutralize the toxicity of the peptide. Taking advantage of controlled radical polymerization and separation, a library of multifunctional oligomers with discrete numbers of functional groups was prepared. Affinity screening revealed that the sequence specificity of the oligomer ligands strongly depended on the number of functional groups. The process reported here will become a general step for the development of abiotic ligands that recognize specific peptide sequences.     

Remote Perfluoroalkyl Substituents are Key to Living Aqueous Ethylene Polymerization

In various nickel(II) salicylaldiminato ethylene polymerization catalysts, which are a versatile mechanistic probe for substituent effects, longer perfluoroalkyl groups exert a strong effect on catalytic activities and polymer microstructures compared to the trifluoromethyl group. This effect is accounted for by a reduced electron density on the active sites, and is also supported by electrochemical studies. Thus, β‐hydride elimination, the key step of chain transfer and branching pathways, is disfavored while chain‐growth rates are enhanced. This enhancement occurs to an extent that enables living polymerizations in aqueous systems to afford ultra‐high‐molecular‐weight polyethylene for various chelating salicylaldimine motifs. These findings are mechanistically instructive as well as practically useful for illustrating the potential of perfluoroalkyl groups in catalyst design.     

Iron‐Catalyzed Highly Enantioselective cis‐Dihydroxylation of Trisubstituted Alkenes with Aqueous H2O2

Reliable methods for enantioselective cis‐dihydroxylation of trisubstituted alkenes are scarce. The iron(II) complex cis‐α‐[Fe^II(2‐Me₂‐BQPN)(OTf)₂], which bears a tetradentate N₄ ligand (Me₂‐BQPN=(R,R)‐N,N′‐dimethyl‐N,N′‐bis(2‐methylquinolin‐8‐yl)‐1,2‐diphenylethane‐1,2‐diamine), was prepared and characterized. With this complex as the catalyst, a broad range of trisubstituted electron‐deficient alkenes were efficiently oxidized to chiral cis‐diols in yields of up to 98 % and up to 99.9 % ee when using hydrogen peroxide (H₂O₂) as oxidant under mild conditions. Experimental studies (including ¹⁸O‐labeling, ESI‐MS, NMR, EPR, and UV/Vis analyses) and DFT calculations were performed to gain mechanistic insight, which suggested possible involvement of a chiral cis‐Fe^V(O)₂ reaction intermediate as an active oxidant. This cis‐[Fe^II(chiral N₄ ligand)]²⁺/H₂O₂ method could be a viable green alternative/complement to the existing OsO₄‐based methods for asymmetric alkene dihydroxylation reactions.     

Atroposelective Synthesis of Axially Chiral N‐Arylpyrroles by Chiral‐at‐Rhodium Catalysis

A transformation of fluxional into configurationally stable axially chiral N‐arylpyrroles was achieved with a highly atroposelective electrophilic aromatic substitution catalyzed by a chiral‐at‐metal rhodium Lewis acid. Specifically, N‐arylpyrroles were alkylated with N‐acryloyl‐1H‐pyrazole electrophiles in up to 93 % yield and with up to >99.5 % ee, and follow‐up conversions reveal the synthetic utility of this new method. DFT calculations elucidate the origins of the observed excellent atroposelectivity.     

Theoretical investigation on submicron particle penetration through circular tubes inside a porous medium

The analytical infinite series solution of submicron particle transport in a circular tube bounded by a porous wall, such as a pinhole, is determined under the slip velocity boundary condition, and the solution is verified by using the experimental data in the previous studies for the specific cases. The results show that particle penetration rate increases with the increase of the porous parameter, the axial pressure drop, and the pinhole radius, whereas it decreases with increasing the pinhole length. The penetration rate of nano-particles are more sensitive to the variation of these parameters. However, the differences between the penetrations of particles ranging from 0.3 μm to 1 μm are not evident because the diffusion becomes weak gradually in this size range. In addition, a further comparison is performed between the analytical solution and the existing studies, and approximate expressions are presented for accurate calculation of particle penetration rate through pinholes appearing in porous materials including filter devices and masks.     

二氧化碳对同质外延生长单晶金刚石内应力的影响

本文研究了在反应气体中引入不同浓度的CO₂对微波等离子体化学气相沉积(MPCVD)法同质外延生长单晶金刚石内应力的影响,并对其作用机理进行了分析。研究发现,随着CO₂浓度增加,单晶金刚石内应力逐渐减小,这是由于添加的CO₂提供了含氧基团,可以有效刻蚀金刚石生长过程中的非金刚石碳,并能够降低金刚石中杂质的含量,从而避免晶格畸变,减少生长缺陷,并最终表现为单晶金刚石内应力的减小,其中金刚石内应力以压应力的形式呈现。此外反应气体中加入CO₂可以降低单晶金刚石的生长速率和沉积温度,且在合适的碳氢氧原子比(5∶112∶4)下能够得到杂质少、结晶度高的单晶金刚石。     

三元层状MAX相固溶体研究进展

MAX相是一类具有层状结构的三元碳化物或(和)氮化物,M是过渡金属元素,A主要是ⅢA~ⅤA族元素,X是C或N元素。这类化合物兼具陶瓷材料和金属材料的特点,具有优异的导电、导热、耐腐蚀以及抗氧化等性能,在诸多领域具有潜在应用价值。近年来,新元素、新结构和固溶体MAX相的不断出现,进一步扩展了MAX相家族。固溶体MAX相是将合适的元素固溶到已知MAX相中而得到的新MAX相。本文分四类总结了127种MAX相固溶体,对其结构改变和性能调控进行了概括,并指出目前研究存在的理论问题和亟须解决的关键技术,最后对MAX相固溶体的发展进行了预测和展望。     

多孔介质(PM)发动机理想循环热力学分析

本文论述了基于多孔介质燃烧技术的超绝热发动机的原理及其工作过程,建立了PM发动机的热力学模型,对 PM发动机内的PM回热循环进行热力学分析,列出了循环参数如压缩比、预胀比、预压比等对发动机效率、循环功的影响,确定了PM回热循环的两种极限状态。将PM回热循环与发动机的Otto循环、Diesel循环进行比较,结果表明: PM回热循环在保证效率的同时,可以大幅度提高循环功。