Crystal structure of octabutyl-μ-dichloro-μ3-dioxodichlorotetratin(IV)

An X-ray diffraction study has shown that Sn atoms in octabutyl-μ-dichloro-μ₃-dioxodichlorotetratin(IV) have distorted trigonal bipyramidal geometry with cis-equatorial butyl groups. Sn(1)C(but) and Sn(2)C(but) bonds are 2.077(21), 2.111(26) and 2.097(23), 2.114(22) Å, respectively. The distances of the triply-bridging O atom from Sn atoms are 2.151(9), 2.018(9) and 2.069(9) Å, and those of the bridging Cl atom are 2.666(5) and 2.831(6) Å. The distance Cl(term)Sn(2) is 2.426(5) Å. Refinement of the structure, based on 1828 observed reflections, converged to an R factor of 0.049 and a weighted R of 0.053. Crystal data for the compound are: a 13.672(6), b 19.529(9), c 8.999(2) Å, β 102.66(3) °, space group P2₁/c, Z = 2, M_r = 1105.49 for [Sn₄(C₄H₉)₈Cl₄O₂], V 2344(2) ų, D_x 1.464 gcm⁻³, F(000) = 1096, λ(Mo-K_α) 0.71069 Å,μ 22.1 cm⁻¹ and T 293 K.     

Redox behavior of trinuclear M3(μ-H)(μ3-μ1:μ2:μ2-C2Fe)(Co)9 and tetranuclear RuM3 3(μ-H)(μ4-μ1:μ1:μ1:μ2-C2Fe)(Co)12 (M=Ru or Os; and Fc=ferrocenyl) clusters. Electronic interaction between the ferrocenylacetylide ligand and the metal core of the cluster

The redox properties of the clusters Ru₃(CO)₁₂(1), Ru₃(μ-H)(μ₃-μ¹:μ²:μ²-C₂Fe)(CO)₉ (2), OS₃(μ-H)(μ₃-μ¹:μ²:μ²-C₂Fe)(CO)₉ (3), Ru₄(μ-H)(μ₄-μ¹:μ¹:μ¹:μ²-C₂Fe)(CO)₁₂ (4), and RuOS₃(μ-H)(μ₄-μ¹:μ¹:μ¹:μ²-C₂Fe)(CO)₁₂ (5) in THF have been studied by cyclic voltammetry in the temperature range from ?60 to +20°C. It was demonstrated that reversible one-electron oxidation of the ferrocenyl fragment in clusters 2–5 occurs at more positive potentials (δE ⁰=0.15–0.26 V) than that of free ferrocene. This is indicative of the electron-withdrawing character of the cluster core with respect to the ferrocenylacetylide ligand. The electron-withdrawing effect of the metal core is more pronounced in tetranuclear clusters4 and 5 than in trinuclear clusters2 and3. Unlike complexes1–3, which undergo irreversible reduction, complexes4 and5 undergo reversible one-electron reduction to form the corresponding radical anions4 ^? and5 ^?.     

μ子自旋旋转(μSR)及其在自由基化学中的应用

1957年人们发现了μ子素M_μ·之后,创立了μ子自旋旋转技术(Muon spin rotation,缩写为μSR),检测M_μ和它的其他形态,研究动力学同位素效应、结构同位素效应和放射化学中的一些课题。1978年人们用μSR技术研究M_μ取代的过渡态有机自由基获得了成功。自此,μSR技术成为一个利用波谱研     

Addition of HCl to a Cluster-Bound Vinylidene Ligand: Preparation and Structure of Ru5(μ3-SMe)(μ3-CMe)(μ-Cl)(μ-SMe)(μ-PPh2)2(CO)9·PhMe

Addition of aqueous HCl to Ru₅( ₃-C=CH₂)(-SMe)₂(-PPh₂)₂(CO)₁₀ afforded the structurally characterized carbyne complex Ru₅( ₃-SMe)( ₃-CMe)(-Cl)(-SMe)(-PPh₂)₂(CO)₉, formed by addition of H to the vinylidene ligand; a Cl atom bridges an Ru–Ru bond.     

SYNTHESIS AND SPECTRAL STUDIES OF(μ-PHENYLTHIO) (μ-ALKYLTHIO) HEXACARBONYLDIIRON COMPLEXES

Through reductive reaction between PhL1 and μ-S2 Fe (CO/6,tollowed by nucleophilicsubstitution of the intermediate (μ-PhS} (μ-LIS} Fe2 (CO)6 toward RX,nine Fe-S clus-ter complexes of (μ-PhS)(μ-RS)Fe2(CO)6 series have been synthesized.The influence of RX structures on the activities in nucleophilic substitution has been examined and possible steroisomers and isomer ratios of the complexes determined.In addition,the regular variations of isomer's CH3-S and CH2-S which are caused by the anisotropic effects of C-O and orientations of unshared electron pairs on sulfurs,have also been preliminarily discussed.     

双簇核铁硫配合物[(μ-RS)Fe2(CO)6]2(μ-S-S-μ)的合成

本文报导由μ-S2F2(CO)6及格氏试剂形成的活泼配合物(1), 可在磺酰氯SO2Cl2的作用下, 发生氧化偶联反应生成由S-S键相连的双簇核配合物(2), 本文对所得配合物(2)的反应性能进行了研究。     

双-μ-氧代-、μ-氧-μ-硫代-和双-μ-硫代-双(半胱氨酸钼)络合物的合成与分离

对Schultz等的μ-氧-μ-硫代-双[(半胱氨酸)氧代钼酸]钠(2)和双-μ-硫代-双[(半胱氨酸)氧代钼酸]钠(3)的合成方法进行了改良。新方法的原料易得,步骤简便。发展了双-μ-氧代双[(半胱氨酸)氧代钼酸]钠(1)和2、3的纸层析分离、纤维粉柱层析和凝胶柱层析分离方法,可以获得纯度高的1、2和3。     

μ-酰基与μ-烯基铁硫原子簇配合物的合成及结构

由芳香族酰氯或α,β-不饱和酰氯与十二羰基三铁-硫醇-三乙胺体系反应,制得了通式为[(μ-RS)(μ-R′CO)Fe,(CO)_6](A)的六个铁硫原子簇配合物,以及通式为((μ-RS)(μR″CH=CR′)Fe_2(CO)_6](B)的六个铁硫配合物。对两种类型的配合物生成的过程及转化进行了初步的讨论。     

配盐[(μ-PhSe)(μ-CO)Fe~2(CO)~6][Et~3NH]的亲电反应研究: (μ-苯硒)(μ-酰基)及(μ-苯硒)(μ-烯基)六羰基二铁配合物的合成及结构

本文研究由Fe_3(CO)_12,PhSeH,Et_3N所形成的配盐[(μ—PhSe)(μ—CO)Fe_2(CO)_6][Et_3NH]与对甲氧基苯甲酰氯、乙酰氯、丙酰氯、苯乙酰氯、α-甲基丙烯酰氯、巴豆酰氯、肉佳酰氯、苯乙炔和β-溴代苯乙烯的反应和机理,合成八个既含μ-苯硒又含μ-酰基或μ-烯基配体的六羰基二铁配合物除用元素分析,MS、IR、~1H NMR表征它们的结构外,尚测得(μ-PhSe)(μ-σ,π-PhCH=CH)Fe_2(CO)_6的单晶结构.该分子单晶的空间群为P2_1/c,晶胞参数α=0.9236(2),b=1.0966(3),c=2.0348(6)nm,β=101.53(1)°,D_x=1.77g/cm~3、Z=4,R=0.054,R_W=0.061     

配盐[(μ-PhSe)(μ-CO)Fe~2(CO)~6][Et~3NH]的亲电反应研究: (μ-苯硒)(μ-酰基)及(μ-苯硒)(μ-烯基)六羰基二铁配合物的合成及结构

本文研究由Fe~3(CO)~1~2, PhSeH, Et~3N所形成的配盐[(μ-PhSe)(μ-CO)Fe~2(CO)~6][Et~3NH]与对甲氧基苯甲酰氯、乙酰氯、丙酰氯、苯乙酰氯、α-甲基丙烯酰氯、巴豆酰氯、肉桂酰氯、苯乙炔和β-溴代苯乙烯的反应和机理, 合成了八个既含μ-苯硒又含μ-酰基或μ-烯基配体的六羰基二铁配合物。除用元素分析、MS、IR、^1H NMR表征它们的结构外, 尚测得(μ-PhSe)(μ-σ,π-PhCH=CH)Fe~2(CO)~6的单晶结构。该分子单晶的空间群为P2~1/c, 晶胞参数a=0.9236(2), b=1.0966(3), c=2.0348(6)nm,β=101.53(1)°, D~x=1.77g/cm^3, Z=4, R=0.054, R~w=0.061。     

Synthesis and characterisation of hexanuclear ruthenium clusters containing a μ4-nitrene ligand. Crystal structures of [Ru6(CO)15(μ-CO)2(μ4NH)(μ-OMe)μ3-η2-N(H)C(O)OMe] and [Ru6(CO)16(μ-CO)2(μ4-NH)(μ-OMe)(μ-NCO)]

Two hexaruthenium carbonyl clusters [Ru₆(CO)₁₅(μ-CO)₂(μ₄-NH) (μ-OMe){μ₃-η²-N(H)C(O)OMe}] and [Ru₆(CO)₁₆(μ-CO)₂-(μ₄-NH)(μ-OMe)(μ-NCO)]2 have been isolated from the pyrolysis of H₂Ru₃(CO))₉NOCH₃, and single-crystal X-ray structure analysis shows that both 1 and 2 have a square planar arrangement of four ruthenium atoms capped by a μ₄-nitrene ligand, with two additional ruthenium atoms bridging two opposite RuRu edges of the square base to form a ‘boat’ form metal framework.     

Crystal structure of [Pd3(μ-OH)(μ-CH3COO)5]

The crystals of the [Pd₃(μ-OH)(μ-CH₃COO)₅] complex are obtained and characterized using powder and single crystal X-ray diffraction and IR spectroscopy. The crystal structure (a = 15.6942(6) Å, b = 11.7190(3) Å, c = 9.7871(3) Å, V = 1800.05(10) ų, space group Pna2₁, Z = 4) is formed from neutral trinuclear cyclic molecules of [Pd₃(μ-OH)(μ-CH₃COO)₅], in which the OH^? group, together with five CH₃COO^? anions, is a bridge ligand.     

SDE-GC-μEGD分析水中挥发性卤代烃

运用微滴溶剂萃取-气相色谱-微池电子捕获检测器联用技术(SDE-GC-μECD)对水中挥发性卤代烃(vHH)的分析进行了可行性探讨,优化了微滴溶剂萃取技术的多种影响因素.方法在0.1～20μg/L之间呈线性,相关系数为0.999 1～0.999 8,相对标准偏差在1.2%～4.6%之间,加标回收率在83%～117%之间.该方法所用的有机溶剂很少(1～2 μL),装置简便,是值得推广的绿色环保、高效的前处理方法.     

新世纪第一次μ-TAS 国际会议

μ-TAS 国内有多种译法,其实质是将分析方法中所用的泵、阀、反应室、相分离器、检测器、控制器预以微型化,并采用微电子工业的加工技术予以一体化,故宜称"微型一体化分析".这是当前分析化学的热点之一,新世纪第一次会议于2000年5月15日至16日在荷兰Twente市召开,由Twente大学主办.内容涉及:(1) 流体体系,(2)细胞分析,(3)微型技术和微型反应室,(4)微流体学,(5)分离系统,(6)单分子和单细胞分析,(7)脱氧核糖酸分析,(8)高产率筛选实验,(9)新观点和其他应用.     

SDE-GC-μECD分析水中挥发性卤代烃

运用微滴溶剂萃取-气相色谱-微池电子捕获检测器联用技术(SDE-GC-μECD)对水中挥发性卤代烃(VHH)的分析进行了可行性探讨,优化了微滴溶剂萃取技术的多种影响因素。方法在0.1~20μg/L之间呈线性,相关系数为0.9991~0.9998,相对标准偏差在1.2%~4.6%之间,加标回收率在83%~117%之间。该方法所用的有机溶剂很少(1~2μL),装置简便,是值得推广的绿色环保、高效的前处理方法。     

双簇核铁硫配合物[(μ-RS)Fe_2(CO)_6]_2(μ-S-S-μ)的合成

双簇核铁硫配合物的研究已引起人们的兴趣,据文献报道,由μ-S_2Fe_2(CO)_6及格氏试剂形成的活泼配合物(1)可在磺酰氯SO_2Cl_2的作用下发生氧化偶联反应,生成由