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181.
The dihydride cluster H_2O_(s_3)(CO)_(10) reacts with ethyne to give a cis-adduct [O_(s_3)H(μ,η~2-CH=CH_2)(CO)_(10)]. The high deuterated cluster D_2O_(s_3)(CO)_(10), the reaction of D_2O_(s_3)(CO)_(10)with ethyne C_2H_2 to form the vinyl product cluster [O_(s_3)D(μ, η~2-CH=CHD)(CO)_(10)], and thereaction of H_2O_(s_3)(CO)_(10) with the deuterated ethyne C_2D_2 to form [O_(s_3)H(μ,η~2-CD=CDH)(CO)_(10)] have been reported primarily in this paper. The two cis-adducts undergo cis-trans-isomerization of μ,η~2-vinyl ligands under a small amount of the nucleophile pyridine. Usingthe combination of deuteration and dynamic ~1H,~2H NMR spectra, we report the experimen-tal evidence determined by the dynamic ~1H, ~2H NMR spectra, mechanism, and kinetic dataof the isomerization. 相似文献
182.
Synthesis and Crystal Structure of [(n‐Bu)4N][W6Cl18] Single‐crystals of [(n‐Bu)4N][W6Cl18] were obtained as thin needles by adding methanol to a solution of W6Cl18 and [(n‐Bu)4N]Cl in tetrahydrofuran. The structure was determined by single‐crystal X‐ray diffraction at 210 K. [(n‐Bu)4N][W6Cl18] crystallizes in the monoclinic space group C 2/c with Z = 8 and the lattice parameters a = 2175.6(1) pm, b = 1738.0(1) pm, c = 2160.36(9) pm, and β = 91.680(5) °. The crystal structure contains isolated [(W6Cl12i)Cl6a]— clusters and [(n‐Bu)4N]+ ions. 相似文献
183.
为了在分子层次上揭示相关催化反应的机理, 人们对过渡金属氧化物团簇与碳氢化合物分子反应进行了大量研究. 相比于过渡金属氧化物团簇阳离子, 阴离子对一些碳氢化合物的活性弱得多, 因此研究还很少. 在本工作中, 我们通过激光溅射产生钒氧团簇阴离子VxOy, 产生的团簇在接近热碰撞条件下与烷烃(C2H6和C4H10)以及烯烃(C2H4和C3H6) 在一个快速流动反应管中进行反应, 飞行时间质谱用来检测反应前后的团簇分布. 在VxOy与烷烃的反应中, 生成了产物V2O6H-和V4O11H-; 在与烯烃的反应中, 产生了相应的吸附产物V4O11X-(X=C2H4或C3H6). 密度泛函理论计算表明: V2O-6和V4O-11可以活化烷烃(C2H6和C4H10)的C—H键, 也可以与烯烃(C2H4和C3H6)发生3+2环化加成反应形成一个五元环结构(-V-O-C-C-O-), C—H键活化与环加成反应都需经历可以克服的反应能垒. 理论计算与实验观测结果相符合. V2O-6和V4O-11团簇都具有氧原子自由基(O·或O-)的成键特征, 活性O-物种也经常出现在钒氧催化剂表面, 因而本研究在分子水平上, 揭示了表面活性氧物种与碳氢化合物反应的机理. 相似文献
184.
A new modification of pulsed-ionization high-pressure mass spectrometry (PHPMS) has been used to perform equilibrium thermochemical studies for relatively nonvolatile biomolecules such as amino acids. Binding enthalpy and entropy changes have been measured for proton-bound clusters of glycine, which are in good agreement with both theoretical (DFT) results of this work and a previous blackbody infrared dissociation experiment. Experimental data indicate that a number of conformers of the proton-bound dimer of glycine may coexist in the explored temperature range (360-460 K). Several new, conceptually different isomers (two of them zwitterionic) have been found by DFT calculations, one of which is 7 kJ mol(-1) lower in energy than the structure previously reported to be the energy minimum. 相似文献
185.
1 INTRODUCTION Trinuclear molybdenum complexes with Mo3(3-S)(-O)n(-S)3n (n = 0~3) cores have been extensively studied on their diversified reactions towards various organic ligands and many metals. Many derivatives with Mo3S4 core have been rationally synthesized from the cation precursor [Mo3S4(H2O)9]4+ and its neutral derivative Mo3(3-S)(-S)3(DTP)4(H2O)[1]. However, due to their structural lability, complexes with Mo3(3-S)(-O)n(-S)3n (n = 1~3) cores have been reported limitedl… 相似文献
186.
Qiutian Liu Chunxi Zhang Changneng Chen Hongping Zhu Yuheng Deng Jinhua Cai 《中国科学B辑(英文版)》1997,40(6):616-623
In a reaction system consisting of FeCl2, tetrathiometallate and cycloalkylthiolate, two Fe4S4 cubanelike cluster compounds were obtained with the following crystallographic data: (PhCH2NMe3)2 [ Fe4S4 (SC5H9)4] (I), monoclinic space groupP21/c,a = 1.632 7(4),b=1.122 9(3),c = 2. 802 5(10) nm, β= 94.63(2)°, Z=4, andR= 0.074; (Et4N)2[F4S4(SC6HlI)4] (II), tetragod space group
,a = l.167 05(9),b = 1.167 06(2),c = 2.063 26(5) nm,Z = 2, Dobs = 1. 28 g/cm3, andR = 0. 078. The participation of cycloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure. Meanwhile, the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.
Project supported by the National Natural Science Foundation of China and the Climbing Program Foundation of China. 相似文献
187.
T. M. Polyanskaya 《Journal of Structural Chemistry》2006,47(5):887-893
A single crystal X-ray diffraction study of a new iodine-containing cluster compound 9-(pyridine)-11-iodo-decahydro-7,8-dicarba-nido-undecaborane [9-C5H5N-11-I-7,8-C2B9H10] has been performed. Crystal data: C7H15B9NI, M = 337.39, monoclinic, space group P21/c, unit cell parameters: a = 9.348(1) Å, b = 11.159(1) Å, c = 13.442(2) Å, β = 98.13(1)°, V = 1388.1(5) Å3, Z = 4, d calc = 1.614 g/cm3, T = 295 K, F(000) = 648, μ = 2.276 mm?1. The structure was solved by a direct method and refined in the full-matrix anisotropic approximation (isotropic for hydrogen atoms) to final agreement factors R 1 = 0.0254, wR 2 = 0.0454 for 2437 I hkl ≥ 2σI from 3590 measured I hkl (an Enraf-Nonius CAD-4 diffractometer, λMoK α , graphite monochromator, θ/2θ-scanning). The molecules are joined into a supramolecular assembly by hydrogen bonds X-H?I (X = B, C). 相似文献
188.
Cao Rong Lei Xin-Jian Hong Mao-Chun Xie Xiu-Lan Kang Bei-Sheng Jiang Fei-Long Liu Qiu-Tian Liu Han-Qin 《结构化学》1995,(1)
Syntheses,StructuresandSpectroscopicPropertiesofMo(W)-Cu-S-ClusterCompoundswithDialkyldithiocarbamateLigandsCaoRong;LeiXin-Ji... 相似文献
189.
以脉冲激光在高真空中溅射钒粉和硫粉的混合物,产生了一系列钒硫原子簇正负离子。根据对其实验记录的激光等离子体质谱进行分析,发现钒硫原子簇的化学键基本上是共价型的,对应于相同钒原子数目的正负离子的相对丰度分别符合于不同形式的对数正态分布。正离子的相对丰度随硫原子数的增加呈对数衰减,由此可以确定各种大小簇合物的簇骼与几何构型;负离子的相对丰度则基本上呈正常的正态分布,说明在簇骼上结合了不同数量硫原子的负离子之结构稳定性大致相近。在实验中还观察到一类硫原子含量较高的簇离子,其中的部分硫原子可能在本身成键形成环状的硫集团后,又与原来的簇骼结合,因而在硫原子数较多时它们的相对丰度符合另一条对数正态分布曲线。 相似文献
190.
The new platinum-osmium alkyne cluster complex Pt2Os4(CO)8(3-PhC2Ph)3 (
4-PhC2Ph),2, was obtained from the reaction of Pt2Os4(CO)18,1b, with PhC2Ph and was characterized by IR.1H NMR and single-crystal X-ray diffraction analyses. The cluster of compound2 consists of an osmium capped Pt2Os3 square pyramid. It aLso contains three triply bridging and one quadruply bridging diphenylacetylene ligands. Crystal data for2: space group PI,a = 12.530(2) Å,b = 21.565(4) Å,c = 11.284(2) Å, = 100.31(2), = 111.89(1), = 76.78(2),Z = 2, 3879 reflections,R = 0.032. 相似文献