Gas‐phase functionalized carbon‐carbon coupling reactions catalyzed by Ni (II) complexes

Gas‐phase C―C coupling reactions mediated by Ni (II) complexes were studied using a linear quadrupole ion trap mass spectrometer. Ternary nickel cationic carboxylate complexes, [(phen)Ni (OOCR¹)]⁺ (where phen = 1,10‐phenanthroline), were formed by electrospray ionization. Upon collision‐induced dissociation (CID), they extrude CO₂ forming the organometallic cation [(phen)Ni(R¹)]⁺, which undergoes gas‐phase ion‐molecule reactions (IMR) with acetate esters CH₃COOR² to yield the acetate complex [(phen)Ni (OOCCH₃)]⁺ and a C―C coupling product R¹‐R². These Ni(II)/phenanthroline‐mediated coupling reactions can be performed with a variety of carbon substituents R¹ and R² (sp³, sp², or aromatic), some of them functionalized. Reaction rates do not seem to be strongly dependent on the nature of the substituents, as sp³‐sp³ or sp²‐sp² coupling reactions proceed rapidly. Experimental results are supported by density functional theory calculations, which provide insights into the energetics associated with the C―C bond coupling step.     

An improved preparation of mesoporous silica‐supported Pd as sustainable catalysts for phosphine‐free Suzuki–Miyaura and Heck coupling reactions

An improved and eco‐friendly procedure has been developed to generate mesoporous silica‐supported palladium nanoparticles (SiO₂@PdNP) that could be used as a sustainable heterogeneous Pd catalyst for phosphine‐free Suzuki–Miyaura and Heck coupling reactions with excellent turnover number and turnover frequency. The presence of Pd on the silica surface was detected by X‐ray diffraction and the structural morphology of SiO₂@PdNP was obtained by transmission electron microscopy. The heterogeneous catalytic system is recyclable and leaching of the metal after the reaction is not apparently observed. Copyright © 2013 John Wiley & Sons, Ltd.     

Palladium‐catalyzed unstrained C(sp3)―N bond activation: the synthesis of N,N‐dimethylacetamide by carbonylation of trimethylamine

This work describes a highly efficient unstrained C(sp³)―N bond activation approach for synthesis of N,N‐dimethylacetamide (DMAc) via catalytic carbonylation of trimethylamine using a PdCl₂/bipy (bipy = 2,2′‐bipyridine)/Me₄NI catalyst system. A low Pd catalyst dosage (1.0 mol%) is sufficient for high selectivity (98.1%) and yield (90.8%), with a turnover number (TON) of 90.0 mmol of DMAc obtained per mmol of PdCl₂ employed under mild reaction conditions. The influence of reaction parameters such as catalyst precursor dosage, ligand type and promoter on activity is investigated. This work also discusses in detail the halide promoter's role in the reaction, and provides a plausible mechanism based on the intermediates methyl iodide and acetyl iodide. Analyses indicate that the carbonylation of trimethylamine may proceed through an active intermediate acetyl iodide formed by carbonylation of methyl iodide generated from the decomposition of the promoter Me₄NI under reaction conditions. The formation of acetyl iodide favors the cleaving efficiency of the inert unstrained C(sp³)―N bond of trimethylamine. Copyright © 2013 John Wiley & Sons, Ltd.     

Pd‐catalyzed homocoupling of arylhydrazines via C―N cleavage under O2

An efficient and simple synthetic method for biaryl synthesis was developed using Pd(OAc)₂ as catalyst from aryl hydrazides under O₂. Various biaryls were synthesized in good yields, offering an expedient protocol for the synthesis of symmetrical biaryl molecules via C―N cleavage. The reactions were performed in component solvent of toluene and acetone without using any pro‐oxidant. Copyright © 2014 John Wiley & Sons, Ltd.     

A tridentate CNO‐donor palladium(II) complex as efficient catalyst for direct C―H arylation: Application in preparation of imidazole‐based push–pull chromophores

A series of imidazolium chlorides for the formation of tridentate CNO‐donor palladium(II) complexes featuring N‐heterocyclic carbene moieties have been developed from cheap and readily available starting materials with high yields. Their palladium complexes were prepared by reactions between the ligand precursors and PdCl₂ using K₂CO₃ as base in pyridine with reasonable yields. These air‐stable metal complexes were characterized using ¹H NMR and ¹³C{¹H} NMR spectroscopy and elemental analyses. Heteronuclear multiple bond correlation experiments were performed to identify key NMR signals of these compounds. The structures of two of the complexes were also established by single‐crystal X‐ray diffraction analysis. One of these complexes was successfully applied in the direct C―H functionalization reactions between heterocyclic compounds and aryl bromides, producing excellent yields of coupled products. The coupling reactions were scalable, allowing grams of coupled products to be obtained with a mere 2 mol% of Pd loading. The catalyst system developed allowed the large‐scale preparation of several push–pull chromophores straightforwardly. Photophysical properties based on UV–visible and fluorescence spectroscopy for these chromophores were investigated. Deep blue photoluminescence with moderate quantum efficiency and twisted intramolecular charge transfer excited state were observed for these chromophores. Density functional theory (DFT) and time‐dependent DFT calculations were performed to support the experimental results.     

Copper activation of boronic acids: factors affecting reactivity

The generation of nucleophiles from the combination of aryl boronic acids and catalytic amounts of copper salt allows a reactivity distinct from other organometallic species, such as organolithiums or Grignard reagents. Here we examine how the electronic and steric properties of the boronic acid affect the formation of active nucleophiles and their subsequent reactivity with iminium‐type compounds, showing that electron‐rich substrates display reduced reactivity. Copyright © 2014 John Wiley & Sons, Ltd.     

基于单片机空气质量检测系统

由粉尘传感器测量空气粉尘浓度,转换成数字量送单片机,单片机分析处理转换成浓度值再与设定浓度值比较;显示器显示空气中粉尘测量浓度和设定浓度;当粉尘浓度超限时,声光报警;     

汉语普通话的管辖音系学特征及提取方法

语音识别中多采用音素作为识别单元,因其数量较多,对神经网络训练复杂度的要求高,在多语言语音识别中需要针对不同语言分别建立识别模块.然而,管辖音系学提出了适用于多语言的语音学特征.本文根据英语和汉语发音的相似性,确定汉语普通话声韵母的GP特征表示形式,并应用神经网络实现特征提取.实验表明,GP特征同样可作为汉语语音的语音学特征.     

ISGP: Iterative sequential geometric programming for precise and robust CMOS analog circuit sizing

In this paper, a fast yet accurate CMOS analog circuit sizing method, referred to as Iterative Sequential Geometric Programming (ISGP), has been proposed. In this methodology, a correction factor has been introduced for each parameter of the geometric programming (GP) compatible device and performance model. These correction factors are updated using a SPICE simulation after every iteration of a sequential geometric programming (SGP) optimization. The proposed methodology takes advantage of SGP based optimization, namely, fast convergence and effectively optimum design and at the same time it uses SPICE simulation to fine tune the design point by rectifying inaccuracy that may exists in the GP compatible device and performance models. In addition, the ISGP considers the requirement of common centroid layout and yield aware design centering for robust final design point specifying the number of fingers and finger widths for each transistor which makes the design point ready for layout.