carbanide,gold(1+) | 128444-79-1

• 分子结构分类: 有机化合物
• 英文名称: carbanide,gold(1+)
• 英文别名: Methylgold
• CAS: 128444-79-1
• 化学式: CH₃Au
• 分子量: 212.001
• InChiKey: CBVLTNAUKASCFM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.58
• 重原子数：
  2.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  cis-dimethyl(phenyl)(triphenylphosphine)gold(III) 以 苯 为溶剂， 生成 carbanide,gold(1+)
  参考文献：
  名称：

  烯基或芳基在从顺式-烯基（或-芳基）二甲基（三苯基膦）金（III）的解离性还原消除上的反常空间效应

  摘要：

  直接与金结合的空间庞大的芳基或烯基抑制了三苯基膦配体从顺-烯基（或-芳基）二甲基（三苯基膦）金（III）的解离速率，从而导致选择性还原消除。

  DOI：

  10.1016/0022-328x(87)83038-3

文献信息

• Infrared spectra of CH3–MH, CH3–M, and CH3–MH− prepared via methane activation by laser-ablated Au, Ag, and Cu atoms
  作者：Han-Gook Cho、Lester Andrews

  DOI：10.1039/c0dt01827a

  日期：——

  Methane activation by laser-ablated, excited Group 11 metal atoms has been carried out, leading to generation of CH3–MH, CH3–M, and CH3–MH−, which are identified in the product infrared spectra on the basis of isotopic shifts and correlation with DFT calculated frequencies. The products reveal that C–H insertion by excited Au, Ag, and Cu readily occurs, and subsequent hydride-detachment or electron addition also follows. Each type of product has similar photochemical properties regardless of the metal. DFT computed energies reveal facile hydride dissociation and high electron affinities for the insertion complexes. The methyl metal species have the shortest C–M bonds, consistent with their highest calculated effective bond order, and the CH3–MH complexes have higher electron affinities than the metal atoms.

  通过激光溅射、激发态的第11族金属原子对甲烷进行活化反应，生成了CH3–MH、 –M和 –MH'，这些产物在红外光谱中根据同位素位移和与DFT计算频率的相关性得到了鉴定。产物表明，激发态的金、银和铜能够容易地进行C–H插入，随后发生氢化物脱离或电子添加。每种类型的产物都具有相似的光化学性质，不受金属种类的影响。DFT计算的能量表明，插入复合物的氢化物解离容易发生，且具有较高的电子亲和性。甲基金属物种的C–M键最短，与其计算出的最高有效键级一致，而 –MH复合物的电子亲和性高于金属原子。
• Gas-Phase Studies of Group-11 Cation (Cu⁺, Ag⁺, and Au⁺) Reactions with 2-Propanol in a Supersonic Beam-Expansion Source
  作者：Ya-Chien Huang、Po-Hua Su、Chen-Sheng Yeh

  DOI：10.1246/bcsj.74.677

  日期：2001.4

  The gas-phase reactions of group-11 ions (Cu+,Ag+, and Au+) with 2-propanol were investigated using laser vaporization combined with supersonic beam expansion in a time-of-flight mass spectrometer. A number of reaction pathways, including assoication, dehydrogenation, and dehydration, were observed. Among these metal ions, Au+ is highly reactive toward 2-propanol. The experimental results are parallel to studies by Wilkins et al. using an FT-ICR mass spectrometer (J. Am. Chem. Soc., 107, 7316 (1985)). The geometries and binding energies of all complexes M+–L, where M+ = Cu+, Ag+ , and Au+, L = 2-propanol, acetone, propene, and H2O, were estimated using Møller–Plesset perturbation (MP2) and density functional theory (BLYP). The bond strengths of the complex ions involving gold revealed the strongest bonding, due to a relativistic effect. The energetic relationship between the reactants and the products facilitated an interpretation of the observed exit channels. Because of the supersonic beam source employed, larger clusters containing metal ions were generated as well. Because the cluster sizes with solvent molecules were ≥ 2, the reactivities were apparently limited to Cu+ and Ag+ clusters, while the reactive nature changed in Au+ along with the formation of acetone, lacking in the bare Au+ reactions. For larger clusters, calculations on Ag+–(2-propanol)2 and Ag+–(2-propanol)(acetone) complexes using BLYP were performed to obtain their energetics.

  对11族离子（Cu+、Ag+和Au+）与2-丙醇的气相反应进行了研究，采用激光蒸发结合超声速束扩展的飞行时间质谱仪。观察到多种反应途径，包括结合、脱氢和脱水。在这些金属离子中，Au+对2-丙醇的反应性最高。实验结果与Wilkins等人使用FT-ICR质谱仪的研究结果相符（J. Am. Chem. Soc., 107, 7316 (1985)）。所有复合物M+–L的几何结构和结合能的估算使用了Møller–Plesset微扰（MP2）和密度泛函理论（BLYP），其中M+ = Cu+、Ag+和Au+，L = 2-丙醇、丙酮、丙烯和H2O。涉及金的复合离子的键强度显示出最强的结合，原因在于相对论效应。反应物与产物之间的能量关系有助于对观察到的反应通道进行解释。由于使用了超声速束源，还生成了包含金属离子的较大簇。由于与溶剂分子的簇大小≥2，反应性显然仅限于Cu+和Ag+簇，而在Au+中反应性质随着丙酮的形成而发生变化，这在裸Au+反应中是缺失的。对于较大的簇，使用BLYP对Ag+–(2-丙醇)2和Ag+–(2-丙醇)(丙酮)复合物进行了能量计算。