[tris(2,4,6-trimethoxyphenyl)phosphine]gold(I) chloride | 164172-67-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [tris(2,4,6-trimethoxyphenyl)phosphine]gold(I) chloride
• 英文别名: (P(2,4,6-trimethoxyphenyl)₃)AuCl；[AuCl(P(2,4,6-trimethoxyphenyl)3)]；[2,4,6-(OMe)₃-Ph]₃PAu-Cl；chloro[tris(2,4,6-trimethoxyphenyl)phosphine]gold(I)；chlorogold;tris(2,4,6-trimethoxyphenyl)phosphane
• CAS: 164172-67-2
• 化学式: C₂₇H₃₃AuClO₉P
• 分子量: 764.947
• InChiKey: NXULLQGFRMGHQH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [tris(2,4,6-trimethoxyphenyl)phosphine]gold(I) chloride 、 在 potassium hydroxide 作用下， 以 二氯甲烷 为溶剂， 反应 0.75h， 以76%的产率得到
  参考文献：
  名称：

  碱促进的质子N-杂环卡宾和无环二氨基卡宾从MnI到AuI的过渡金属化反应：机理研究

  摘要：

  DFT theoretical calculations for the base-induced transmetalation process of protic N-heterocyclic carbenes of imidazol-2-ylidene type from Mn(I) to Au(I) have been carried out. The reaction mechanism found involves the formation of key reaction intermediates bearing a pure bridging imidazolyl ligand between manganese and gold, as well as transition states showing eta(2) coordination of this ligand, first to gold and then to manganese, before the transmetalation process is completed. In addition, similar DFT calculations have been performed on protic acyclic diamino carbene complexes, showing analogous transferring of the carbene moiety from Mn(I) to Au(I) to afford remarkable mangana-N-heterocyclic carbenes of gold.

  DOI：

  10.1021/acs.organomet.7b00009
• 作为产物：
  描述：

  氯(二甲基硫化)金(I) 、 三(2,4,6-三甲氧基苯基)磷 以 乙醇 为溶剂， 以63%的产率得到[tris(2,4,6-trimethoxyphenyl)phosphine]gold(I) chloride
  参考文献：
  名称：

  三（2,4,6-三甲氧基苯基）膦与卤化金（I）的两个坐标配合物的结构，远红外和31 P核磁共振研究

  摘要：

  配合物[AuX（tmpp）] [X = Cl，Br或I; 通过tmpp与[AuX（Me 2 S）]或[AuX 2 ] –反应制备tmpp =三（2,4,6-三甲氧基苯基）膦。结晶化合物是同构的，具有相应的Cu和Ag配合物，Au–P 2.253（5），2.255（4），2.239（7），Au–X 2.303（6），2.413（2），2.586（2） Å和P–Au–X 176.0（2），175.9（1），177.7（2）°。涉及配体中三个苯基上最接近的邻甲氧基氧原子的Au⋯O接触为：3.15（1），3.08（1），2.92（2）（氯化物）；3.13（2），3.11（1），2.96（1）（溴化物）；3.01（2），3.10（1），3.09（2）Å（碘化物）。配合物[AuX（tmpp）]通过远红外光谱[ν（Au–X）313，218，183 cm –1表征。; X = Cl，Br，I]并乘以31乙腈中的P

  DOI：

  10.1039/dt9950001341

文献信息

• Synthesis of L–Au(I)–CF₂H Complexes and Their Application as Transmetalation Shuttles to the Difluoromethylation of Aryl Iodides
  作者：Patricia García-Domínguez

  DOI：10.1021/acs.organomet.1c00305

  日期：2021.9.13

  formed in the presence of base, have been identified as intermediate complexes involved in these transformations. The application of these compounds as “CF2H transmetalation shuttles” from gold to palladium has been demonstrated in a Pd-catalyzed difluoromethylation reaction of aryl iodides, in which the Au-to-Pd transfer of “CF2H” is feasible under stoichiometric conditions. These findings will pave the

  我们在此描述了两种替代方案，以有效地制备带有不同电子和空间特性的辅助配体的二氟甲基金 (I) 配合物。LAu-OX（X = H 和t- Bu）物质在碱存在下形成，已被确定为参与这些转化的中间复合物。这些化合物作为从金到钯的“CF 2 H 金属转移穿梭”的应用已在 Pd 催化的芳基碘化物的二氟甲基化反应中得到证明，其中“CF 2 H”的 Au 到 Pd 的转移在化学计量下是可行的状况。这些发现将为金化学中的催化歧管铺平道路。
• A combined NMR/DFT study on the ion pair structure of [(PR¹₂R²)Au(η²-3-hexyne)]BF₄complexes
  作者：Gianluca Ciancaleoni、Leonardo Belpassi、Francesco Tarantelli、Daniele Zuccaccia、Alceo Macchioni

  DOI：10.1039/c2dt32260a

  日期：——

  The interionic structure of four gold(I) π-alkyne ion pairs, with general formula [(PR12R2)Au(η2-3-hexyne)]BF4 (R1 = R2 = tBu, 1a; R1 = tBu, R2 = o-diphenyl, 2a; R1 = R2 = 2,4,6-trimethoxyphenyl, 3a; R1 = R2 = 2,4-di-tert-butylphenoxy, 4a), was studied by 19F, 1H-HOESY NMR spectroscopy. In all the cases the anion locates mainly close to the alkyne, but the degree of specificity of location strongly depends on the P-ligand and it is high for ion pairs bearing poorly electron donating PR12R2 ligands (particularly, 4a) and low for ion pairs with strongly electron donating PR12R2 ones (such as 3a). This result is rationalized through relativistic DFT calculations, showing that the electronic properties of the P-ligand finely tune the charge accumulation on the alkyne and, consequently, its ability of attracting the anion.

  通过 19F、1H-HOESY NMR 光谱研究了通式为 [(PR12R2)Au(δ-2-3-己炔)]BF4（R1 = R2 = tBu，1a；R1 = tBu，R2 = 邻二苯基，2a；R1 = R2 = 2,4,6-三甲氧基苯基，3a；R1 = R2 = 2,4-二叔丁基苯氧基，4a）的四个金（I）Ï-炔离子对的离子间结构。在所有情况下，阴离子的位置都主要靠近炔烃，但位置的特异性程度在很大程度上取决于 P 配体，对于带有电子捐赠性差的 PR12R2 配体的离子对（尤其是 4a），其特异性程度较高，而对于带有强电子捐赠性 PR12R2 配体的离子对（如 3a），其特异性程度较低。相对论 DFT 计算证明了这一结果的合理性，表明 P 配体的电子特性可微调炔烃上的电荷积累，从而微调其吸引阴离子的能力。
• X-ray structural determination of a bulky phosphine complex: chloro{tris(2,4,6-trimethoxyphenyl)phosphine}gold(I), {AuCl[P(C9H11O3)3]}
  作者：Elmer C Alyea、George Ferguson、Shanmugaperumal Kannan

  DOI：10.1016/s0277-5387(00)00527-1

  日期：2000.10

  The title compound, AuCl[P(C9H11O3)(3)]}, has three fold symmetry in the solid state. The Au Cl and Au-P bond lengths are 2.294 and 2.255 Angstrom, respectively, and the Au atom has nearly linear coordination geometry, with P Au Cl 176.03(9)degrees The extreme bulkiness of the phosphine ligand is shown by the mean cone angle of 188 degrees (based on O atoms defining the cone), though the cone angle is considerably smaller than 214 degrees for trimesitylphosphine in the known analogous complex. The shorter Au-P bond distance than for Ag-P (2.379(1) Angstrom) in the corresponding known silver chloride complex of tris(2.4,6-trimethoxyphenyl)phosphine tentatively supports an earlier conclusion that gold is smaller than silver. (C) 2000 Elsevier Science B.V. All rights reserved.