α-Telluration of 2-acetylthiophene: Electronic influence of the heteroaromatic moiety on solid state structures

Room temperature oxidative addition of α-bromo-2-acetylthiophene to elemental tellurium and aryltellurium(II) bromide provides direct routes to (2-thiophenoylmethyl)tellurium(IV) dibromides, (2-(C₄H₃S)COCH₂)₂TeBr₂ (1b) and 2-(C₄H₃S)COCH₂ArTeBr₂ (Ar = 1-C₁₀H₇, Npl, 2b; 2,4,6-Me₃C₆H₂, Mes, 3b). The chloro analogues, 2-(C₄H₃S)COCH₂ArTeCl₂ (Ar = Npl, 2a; Mes, 3a) were prepared by the condensation reaction of the parent methyl ketone with NplTeCl₃ or MesTeCl₃. Metathesis of these products with an alkali iodide affords the iodo analogues 1c, 2c and 3c. These diorganotellurium dihalides are reduced with aqueous bisulfite to diorganotellurides 1-3, which can be oxidized readily with dihalogens to the desired diorganotellurium(IV) dihalides. Compound 1 is a rare example of a symmetrical telluroether with C_sp3-Te-C_sp3 grouping that has been characterized by single-crystal diffraction techniques. Preference of the 2-thiophenoylmethyl ligand for small-bite (C, O) chelation over less strained (C, S) coordination is evident in the crystal structures of the Te(IV) compounds 1b, 2a, 2b and 3a. The unexpected transoidal orientation of the two acylmethyl ligands in the solid state molecular configuration of symmetrical diorganotellurium(IV) dibromide 1b appears to be a combined effect of electronic repulsion due to the thiophene moieties and steric repulsion of bromo ligands.     

Reactivity of ortho‐Substituted Aryl–Palladium Complexes towards Carbodiimides,Isothiocyanates, Nitriles,and Cyanamides

Complexes [Pd(C₆H₃XH‐2‐R′‐5)Y(N^N)] (X=O, NH; Y=Br, I; R′=H, NO₂; N^N=N,N,N′,N′‐tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine (dtbbpy)) react with RN?C?E (E=NR, S) or RC≡N (R=alkyl, aryl, NR′′₂) and TlOTf (OTf=CF₃SO₃) to give, respectively, 1) products of the insertion of the C?E group into the C? Pd bond, protonation of the N atom, and coordination of X to Pd, [Pd{κ²‐X,E‐(XC₆H₃{EC(NHR)}‐2‐R′‐4)}(N^N)]OTf or [Pd(κ²‐X,N‐{ZC₆H₃(NH?CR)‐2‐R′‐4})(N^N)]OTf, or products of the coordination of carbodiimides and OH addition, [Pd{κ²‐C,N‐(C₆H₄{OC(NR)}NHR‐2)}(bpy)]OTf; or 2) products of the insertion of the C≡N group to Pd and N‐protonation, [Pd(κ²‐X,N‐{XC₆H₃(NH?CR)‐2‐R′‐4})(N^N)]OTf.     

Two Distinct Mechanisms of Alkyne Insertion into the Metal–Sulfur Bond: Combined Experimental and Theoretical Study and Application in Catalysis

The present study reports the evidence for the multiple carbon–carbon bond insertion into the metal–heteroatom bond via a five‐coordinate metal complex. Detailed analysis of the model catalytic reaction of the carbon–sulfur (C? S) bond formation unveiled the mechanism of metal‐mediated alkyne insertion: a new pathway of C? S bond formation without preliminary ligand dissociation was revealed based on experimental and theoretical investigations. According to this pathway alkyne insertion into the metal–sulfur bond led to the formation of intermediate metal complex capable of direct C? S reductive elimination. In contrast, an intermediate metal complex formed through alkyne insertion through the traditional pathway involving preliminary ligand dissociation suffered from “improper” geometry configuration, which may block the whole catalytic cycle. A new catalytic system was developed to solve the problem of stereoselective S? S bond addition to internal alkynes and a cost‐efficient Ni‐catalyzed synthetic procedure is reported to furnish formation of target vinyl sulfides with high yields (up to 99 %) and excellent Z/E selectivity (>99:1).     

电源线滤波器对电子设备EMC影响分析

针对电子设备在电磁兼容(Electromagnetic Compatibility,EMC)测试中遇到的问题,从电源线滤波器内部电路入手,分析了电源线滤波器对电子设备EMC性能的影响。描述了如何根据电子设备内部电路、使用条件,尤其是输入端电路特性,对电源线滤波器的阻抗特性、插入损耗等参数进行正确选择。对于影响电子设备EMC性能的电源线滤波器的安装方法进行了分析、讨论,列举了2个实际测试例子,并对整改措施进行描述和分析。     

3dB带状线电桥的研究与设计

首先对90°电桥进行了分析。提出一种特殊结构的宽带3dB电桥的设计方案。该方案可使电桥方向性更好、制作工艺更加简便,其带宽可达到9～11GHz,可以承受较大的功率容量,体积小,新式结构使其实现了低插损、高方向性和宽频带,并且易生产、易调试。实测结果和仿真结果基本吻合,验证了研究结果的一致性。     

开关电源输入EMI滤波器设计与仿真

开关电源中常用EMI滤波器抑制共模干扰和差模干扰。三端电容器在抑制开关电源高频干扰方面有良好性能。文中在开关电源一般性能EMI滤波器电路结构基础上,给出了使用三端电容器抑制高频噪声的滤波器结构。并使用PSpice软件对插入损耗进行仿真,给出了仿真结果。     

Crystal structure and properties of a new mixed-valence compound LiMn2TeO6 and the survey of the LiMM′XO6 family (X = Sb or Te)

A new compound, LiMn²⁺Mn³⁺TeO₆, was prepared by solid-state reactions and characterized by powder X-ray diffraction, redox titration, conductivity, magnetic measurements and cycling behaviour in an electrochemical cell with Li counter electrode. It is triclinic, P1, a = 5.1077(1), b = 8.5707(1), c = 5.0589(1), α = 92.515(1)°, β = 92.092(2)°, γ = 89.818(2)°, Z = 2. The structure is based on strongly distorted hexagonal close packing of oxygen anions with cations occupying octahedral voids and represents the ordered variant of orthorhombic Li₂TiTeO₆ structure, derived from LiSbO₃. TeO₆ octahedra are almost regular but all four independent MnO₆ octahedra display severe distortions. Room-temperature conductivity is unexpectedly low for a mixed-valence compound, 2 × 10⁻⁷ S/cm. Together with the observed antiferromagnetic exchange interaction, this is a prerequisite for the colossal magnetoresistance effect. The unit cell volumes of LiMn₂TeO₆, LiSbO₃, Li₂M⁴⁺TeO₆ and LiMM′XO₆ series (a total of 21 compounds) correlate well with average cationic radii, but LiMn₂SbO₆ deviates considerably, and its preparation could not be reproduced.     

ON THE MECHANISM OF PHOTOCHEMICAL ALKYNE INSERTION INTO CYCLOPENTADIENYLIRONDICARBONYL DIMER: ALKYNE ADDITION TO A “TIED-BACK” Cp-Fe DIMER

Abstract

The photochemical insertion of phenylacetylene with the “tied-back” dinuclear complex [(η⁵-C₅H₄)₂SiMe₂]Fe₂(CO)₂(μ-CO)₂ (4) yields, by X-ray structural analysis, a dimetallacyclopentenone product entirely analogous to that obtained from the photochemical reaction of the alkyne with (η⁵ - C₅H₅)₂Fe₂(CO)₂(μ-CO)₂ (1). This result is interpreted as evidence for an alternative pathway for photochemical alkyne addition to 1. Attempts to identify the photochemical intermediates from 4 have been unsuccessful. A competition study between 1 and 4 indicates that photochemical alkyne insertion into 1 is preferred by approximate ratio of 2:1 over insertion into 4.