[(tris(3,5-bis(trifluoromethyl)phenyl)phosphine)AuCl] | 385815-84-9

• 英文名称: [(tris(3,5-bis(trifluoromethyl)phenyl)phosphine)AuCl]
• 英文别名: (tris(3,5-bis(trifluoromethyl)phenyl)phosphine)gold chloride；chloro[tris(3,5-bis-(trifluoromethyl)phenyl)phosphine]gold；[(PArF)AuCl]；((3,5-bis(frifluoromethyl)phenyl)3P)AuCl；(3,5-(F3C)2C6H3)3PAuCl
• CAS: 385815-84-9
• 化学式: C₂₄H₉AuClF₁₈P
• 分子量: 902.7
• InChiKey: IBLRYIACSLPBRA-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：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(tris(3,5-bis(trifluoromethyl)phenyl)phosphine)AuCl] 、 silver trifluoromethanesulfonate 以 二氯甲烷 为溶剂， 反应 1.0h， 以91%的产率得到
  参考文献：
  名称：

  Toward Optimizing the Performance of Homogeneous L-Au-X Catalysts through Appropriate Matching of the Ligand (L) and Counterion (X^–)

  摘要：

  The effects of the ligand (L) and counterion (X-) are considered the two most important factors in homogeneous gold catalysis, but a rational understanding of their synergy/antagonism is still lacking. In this work, we synthesized a set of 16 gold-complexes of the type L-Au-X that differ as follows: (i) L = PPh3 (Li), P(Bu-t)(3) (L2), tris(3,5-bis(trifluoromethyl)phenyl)phosphine (PArF, L3), and 1,3-bis (2,6-diisopropylphenyl)imidazol-2-ylidene (NHC, L4), with the deliberate purpose of varying the electron withdrawing ability of the ligand, and (ii) X- = BF4-, OTf-, OTs-, and TFA(-), which have various coordinating abilities, basicities, and hydrogen bond acceptor powers. All these catalysts were tested in two different model reactions: the cycloisomerization of N-(prop-2-ynyl)benzamide to 2-phenyl-5-vinylidene-2-oxazoline and the methoxylation of 3-hexyne. The main results are that the choice of the most efficient L-Au-X catalyst for a given process should not be made by evaluating the properties of L and X- alone, but rather based on their best combination. For NHC-Au-X, the noncoordinating and weakly basic anions (such as BF4- and OTf-) have been recognized as the best choice for the cycloisomerization of N-(prop-2-ynyl)benzamide. On the other side, the intermediate coordinating ability and basicity of OTs- provide the best compromise for achieving an efficient methoxylation of 3-hexyne. A completely different trend is found in the case of complexes bearing phosphanes: OTs- and TFA(-) have been found to accelerate the c-ydoisomerization of N-(prop-2-ynyl)benzamide, and BF4- and OTf- are suitable for the methoxylation of 3-hexyne. A possible explanation of the observed differences between phosphane and NBC ancillary ligands might be found in the higher affinity of the counterion (especially OTs-) for the gold fragment for phosphane instead of NHC.

  DOI：

  10.1021/acs.organomet.5b00308
• 作为产物：
  描述：

  四氯金酸水合物 、 三[3,4-双(三氟甲基)苯基]膦 在 β-thiodiglucol 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 以98.6%的产率得到[(tris(3,5-bis(trifluoromethyl)phenyl)phosphine)AuCl]
  参考文献：
  名称：

  取代基对芳基膦-Au（I）衍生物晶体中的亲酸性和π-π相互作用的影响。化合物（CX3C6H4）3PAuandX和{（CF3）2C6H3}3PAuX的合成及X射线结构研究

  摘要：

  摘要：通过单晶X射线衍射方法研究了一系列单齿膦，R'3PAuX（X = Cl，Sph和Spy）的Au（I）配合物对取代基的亲和力相互作用的影响。当在（C 6 H 5）3 P中的苯环的间位引入CF 3取代基时，在ClAuP（m -CF 3 C 6 H 4）3中产生亲油性。然而，通过在两个间位引入两个CF 3基团，弱亲性已经减弱。当CF 3取代基取代对位上的H原子时或当CH 3取代基被引入间位和/或对位时，对于R'3 PAuCl和R'3 PAuSph没有观察到这种效果。通过嗜酸性构建的大多数二聚体似乎被Sph配体的苯环或Spy配体的吡啶环与R'3 P配体中的一个苯环之间的π-π相互作用所增强。在{3,5-（F 3 C）2 C 6 H 3} 3 PAuSph晶体中创建了一种新颖的梯形超分子结构，在（C 6 H 5）3 PAuSpy晶体中形成了四聚体。通过亲酸和π-π相互作用。已经讨论了取代基对重要键长的影响。

  DOI：

  10.1016/s0020-1693(01)00543-6
• 作为试剂：
  描述：

  2-碘苯-1-磺酰氯 在 bis-triphenylphosphine-palladium(II) chloride 、 ammonium hydroxide 、 copper(l) iodide 、 [(tris(3,5-bis(trifluoromethyl)phenyl)phosphine)AuCl] 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 为溶剂， 反应 19.08h， 生成 4-(4-bromophenyl)-3-(4-methoxyphenyl)-2H-benzo[e][1,2]thiazine 1,1-dioxide 、 (E)-4-(2-(4-bromophenyl)hydrazineylidene)-3-(4-methoxyphenyl)-4H-benzo[e][1,2]thiazine 1,1-dioxide
  参考文献：
  名称：

  金催化邻炔基苯磺酰胺与芳基重氮盐双官能化的可切换发散合成

  摘要：

  本文报道了金催化的邻炔基苯磺酰胺与芳基重氮盐的双官能化。在用蓝色 LED 照射后，苯磺舒坦产物通过氨基芳基化形成，伴随着 N 2的释放。在没有辐照的情况下，芳基重氮盐作为有效的亲电试剂，促进乙烯基-Au(I) 中间体的亲电脱氢，然后互变异构化得到N-芳基取代的 α-亚氨基 ( E )-腙。6 -endo-dig和 5 -exo-dig环化的区域选择性非常好。

  DOI：

  10.1021/acs.orglett.1c02621

文献信息

• Synthesis of<i>gem</i>-Diaurated Species from Alkynols
  作者：Alexander Zhdanko、Martin E. Maier

  DOI：10.1002/chem.201204491

  日期：2013.3.18

  A number of enol ether‐derived diaurated species were synthesized directly from different alkynols and cationic gold complexes in the presence of a non‐nucleophilic base (proton sponge). The reaction can be easily applied for in situ generation of diaurated species from all common types of hydroalkoxylation substrates: 5‐endo, 5‐exo/6‐endo, 6‐exo/7‐endo and intermolecular types. Six examples were also

  在非亲核碱（质子海绵）存在的情况下，由不同的炔醇和阳离子金络合物直接合成了许多烯醇醚衍生的弱化物种。该反应可轻松用于从所有常见类型的加氢烷氧基化底物上原位生成加氢物种：5-内，5-外// 6-内，6-外/ 7-内和分子间类型。还以稳定状态的六氟锑酸盐的形式单独合成了六个实例。尽管从所有常规单核金催化剂中都能可靠地获得低价物质，但使用双核金催化剂通常会得到具有不同性质的低价物质。初步结果指出了双核金催化剂行为的复杂性，将来需要对该子类进行更多的研究。还研究了由各种金-氧化合物（LAu）2 OH +，（LAu）3 O +和LAuOH（L =膦配体）形成的弱化物种。在这三种类型中，只有（LAu）2 OH +具有反应性，而（LAu）3 O +LAuOH和LAuOH本身不具有反应性，但需要酸性助催化剂才能进行反应。这些化合物的反应能力差异是由这些化合物生成必要的乙炔π-复杂中间体的能力解释的。
• Cyclization of 2-Alkynyldimethylaniline on Gold(I) Cationic and Neutral Complexes
  作者：Luca Biasiolo、Leonardo Belpassi、Carlo Alberto Gaggioli、Alceo Macchioni、Francesco Tarantelli、Gianluca Ciancaleoni、Daniele Zuccaccia

  DOI：10.1021/acs.organomet.5b01030

  日期：2016.2.22

  The cyclization reaction of 2-(1-hexynyl)dimethylaniline (S) on gold(I) has been studied by NMR spectroscopy, in order to characterize the ion pair structure of the product, [LAuSc]BF4. The latter is a good model for the catalytic intermediate between the nucleophilic attack and the protodeauration step of a typical gold catalytic cycle. F-19, H-1 HOESY NMR results demonstrate that in [LAuSc]BF4, with L being three different ligands, the anion mainly interacts with the ammonium moiety of the substrate, thanks to its formal positive charge, even if the ligand can tune the exact position of the anion. Furthermore, also gold chloride is able to promote the cyclization of S, forming [ClAuSc], which is the first example of a new class of precatalysts with potentially interesting catalytic properties. Preliminary data on its catalytic performances and a detailed DFT characterization of its electronic properties are presented, both of which indicate that S-c behaves as a carbene.
• A Phosphine Gold(I) π-Alkyne Complex: Tuning the Metal−Alkyne Bond Character and Counterion Position by the Choice of the Ancillary Ligand
  作者：Daniele Zuccaccia、Leonardo Belpassi、Luca Rocchigiani、Francesco Tarantelli、Alceo Macchioni

  DOI：10.1021/ic100093n

  日期：2010.4.5

  The intra- and interionic structures of a mononuclear phosphine gold(I) alkyne complex [(PAr3F)Au(2-hexyne)]BF4 [1BF4; Ar-F = 3,5-bis(trifluoromethyl)phenyl] and its analogous complex [(NHC)Au- (2-hexyne)]BF4 [2BF(4); NHC = 1,3-bis(dilsopropylphenyl)imidazol-2-ylidene] have been investigated by combining 1D and 20 multinuclear NMR spectroscopy and density functional theory calculations. It has been found that alkyne in 1BF(4) is depleted of its electron density to a greater extent than that in 2BF(4). This correlates with the Delta delta(C-13) NMR of the carbon carbon triple bond. Instead, 2BF(4) is much more "kinetically stable" than 1BF(4). F-19-H-1 HOESY NMR experiments indicate that the counterion locates close to the gold atom in 1BF(4) (differently from that previously observed in the few other gold(I) ion pairs studied), exactly where the computed Coulomb potential indicates that partial positive charge accumulates.