bis(triphenylphosphine)gold(I) triflate | 61359-40-8

• 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: bis(triphenylphosphine)gold(I) triflate
• 英文别名: [Au(P(C6H5)3)2](triflate)；[Au(PPh₃)₂]OTf；[Au(triphenylphosphine)2]OTf；[(Ph3P)2Au](triflate)
• CAS: 61359-40-8；147141-54-6
• 化学式: CF₃O₃S*C₃₆H₃₀AuP₂
• 分子量: 870.619
• InChiKey: ZCOQNCVQEWRGOT-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.94
• 重原子数：
  47.0
• 可旋转键数：
  8.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  57.2
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  bis(triphenylphosphine)gold(I) triflate 、 [Au(C₆F₅){C(PPh₃)C=CH₂}] 以 二氯甲烷 为溶剂， 反应 0.5h， 以50%的产率得到[Au(PPh₃){C(PPh₃)C=CH₂}](OTf)
  参考文献：
  名称：

  Axially Chiral Allenyl Gold Complexes

  摘要：

  Unprecedented allenyl gold complexes have been achieved starting from triphenylpropargylphosphonium bromide. Two different coordination modes of the allene isomer of triphenylphosphoniumpropargylide to gold have been found depending on the gold oxidation state. Bromo-, pentafluorophenyl-, and triphenylphosphine-gold(I) allenyl complexes were prepared in which the α carbon coordinates to the gold(I) center. A chiral pentafluorophenyl-gold(III) allenyl complex with the gold atoms coordinated to the γ carbon was also prepared. All the complexes have been structurally characterized by X-ray diffraction showing the characteristic distances for a C═C═C unit.

  DOI：

  10.1021/ja5055675
• 作为产物：
  描述：

  trans-[Au(CF₃)Me₂(PPh₃)] 以 二氯甲烷 、 氘代甲苯 为溶剂， 反应 27.33h， 生成 bis(triphenylphosphine)gold(I) triflate
  参考文献：
  名称：

  导致 C(sp3)–X（X = C、N、P、O、卤素）键形成的金 (III) 配合物中的还原消除反应：内球与 SN2 途径

  摘要：

  导致在 Au(III) 配合物的配位层中形成 C-杂原子键的反应并不常见，其机制尚不为人所知。这项工作报告了一系列含有不同 Au-杂原子键的 Au(III) 甲基配合物的合成和还原消除反应。配合物 [Au(CF 3 )(Me)(X)(PR 3 )] (R = Ph, X = OTf, OClO 3 , ONO 2 , OC(O)CF 3 , F, Cl, Br; R = Cy, X = Me, OTf, Br)是通过反式-[Au(CF 3 )(Me) 2 (PR 3 )] (R = Ph, Cy)与HX的反应得到的。阳离子络合物cis -[Au(CF 3 )(Me)(PPh3 ) 2 ]OTf由[Au(CF 3 )(Me)(OTf)(PPh 3 )]与PPh 3反应得到。加热这些复合物导致 MeX（X = Me、Ph 3 P +、OTf、OClO 3、ONO 2、OC(O)CF 3、F、C

  DOI：

  10.1021/acs.inorgchem.2c04166

文献信息

• Synthesis of Gold(I) and Gold(II) Complexes with Diphenyl(trimethylsilylmethyl)phosphane
  作者：Manuel Bardají、Peter G. Jones、Antonio Laguna

  DOI：10.1002/(sici)1099-0682(199807)1998:7<989::aid-ejic989>3.0.co;2-n

  日期：1998.7

  symmetrical derivatives [Au(PPh2R)2](CF3SO3) (R = Ph, CH2-SiMe3). The molecular structure of complex 3 has been established by X-ray diffraction and shows an antiperiplanar arrangement of the two PR2R rotors in the solid state. The reaction of the phosphane ligand with [Au2μ-(CH2)2-PPh2}2(tht)2](ClO4)2affords the dinuclear gold(II) complex [Au2μ-(CH2)2PPh2}2(PPh2CH2SiMe3)2](ClO4)2 (5).

  二苯基（三甲基甲硅烷基甲基）膦与 [AuCl(tht)] 反应得到金 (I) 配合物 [AuCl(PPh2- SiMe3)] (1) 或 [Au(PPh2 SiMe3)2]Cl (2)。对 1 的 X 射线研究没有揭示任何 Au……Au 相互作用。用二苯基（三甲基甲硅烷基甲基）磷烷处理 [Au(tht)2](CF3SO3) 或 [Au(tht)(PPh3)](CF3SO3) 导致硫醚配体的置换，得到离子复合物 [Au(PPh2 SiMe3)2 ](CF3SO3) (3) 或 [Au(PPh2- SiMe3)(PPh3)](CF3SO3) (4)，后者与对称衍生物混合 [Au(PPh2R)2](CF3SO3) (R = Ph, CH2- SiMe3)。配合物 3 的分子结构已通过 X 射线衍射确定，并显示出固态的两个 PR2R 转子的反周面排列。
• Coordination Chemistry of Gold Catalysts in Solution: A Detailed NMR Study
  作者：Alexander Zhdanko、Markus Ströbele、Martin E. Maier

  DOI：10.1002/chem.201201215

  日期：2012.11.12

  Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh3, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For

  已通过NMR光谱在室内溶液中研究了带有八种不同配体[L = PPh 3，JohnPhos（L2），Xphos（L3），DTBP，IMes，IPr，dppf，S- tolBINAP（L8）的金催化剂的配位化学温度。阳离子或中性单核复合物LAuX（L = L2，L3，IMes，IPr; X =带电或中性配体）进行简单的配体交换而没有给出任何更高的配位络合物。对于L2 AUX测定以下配体强度系列：MeOH«hex-3-炔
• Alkyne/Alkene/Allene-Induced Disproportionation of Cationic Gold(I) Catalyst
  作者：Manish Kumar、Jacek Jasinski、Gerald B. Hammond、Bo Xu

  DOI：10.1002/chem.201304271

  日期：2014.3.10

  experimental study of the deactivation of cationic gold was conducted, and the influence of each component in the reaction system (substrate, counterion, solvent) on the decay process was examined. It was found that a substrate (alkyne/allene/alkene)‐induced disproportionation of gold(I) may play a key role in the decay process. Our mechanism is supported by kinetic, XPS, voltammetry studies, and high‐resolution

  阳离子金失活的第一详细的实验研究进行，并检测在衰变过程中反应系统（基材，抗衡离子，溶剂）各成分的影响。发现底物（炔烃/丙二烯/烯烃）诱导的金（I）歧化可能在衰变过程中起关键作用。动力学，XPS，伏安法研究和高分辨率ESI-MS数据为我们的机理提供了支持。
• Group 11 complexes with unsymmetrical P,S and P,Se disubstituted ferrocene ligands
  作者：Javier E. Aguado、Silvia Canales、M. Concepción Gimeno、Peter G. Jones、Antonio Laguna、M. Dolores Villacampa

  DOI：10.1039/b507058a

  日期：——

  with several group 11 metal derivatives leads to the synthesis of complexes of the type [MXFc(EPh)PPh2}](M = Au, X = Cl, C6F5; M = Ag, X = OTf), (OTf = trifluoromethanesulfonate), [MFc(EPh)PPh2}2]X (M = Au, X = ClO4; M = Ag, X = OTf), [M(PPh3)Fc(EPh)PPh2}]OTf (M = Au, Ag), [Au2Fc(SPh)PPh2}2](ClO4)2, [Au(C6F5)2Fc(SePh)PPh2}]ClO4, [Au(C6F5)3Fc(EPh)PPh2}], [Au2(C6F5)6Fc(SePh)PPh2}] or [CuFc(EPh)PPh2}2]PF6(E

  非对称配体1-二苯基膦-1'-（苯基硫烷基）二茂铁与1-二苯基膦-1'-（苯基硒烯基）二茂铁Fc（EPh）PPh2（E = S，Se）与几种11族金属衍生物的反应合成[MX Fc（EPh）PPh2}]类型的配合物（M = Au，X = Cl，C6F5； M = Ag，X = OTf），（OTf =三氟甲磺酸盐），[M Fc（EPh ）PPh2} 2] X（M = Au，X = ClO4; M = Ag，X = OTf），[M（PPh3）Fc（EPh）PPh2}] OTf（M = Au，Ag），[Au2 Fc （SPh）PPh2} 2]（ ）2，[Au（ ）2 Fc（SePh）PPh2}] ，[Au（ ）3 Fc（EPh）PPh2}]，[Au2（ ）6 Fc（SePh）PPh2}]或[Cu Fc（EPh）PPh2} 2] PF6（E = S，
• Ligand Effects and Ligand Design in Homogeneous Gold(I) Catalysis
  作者：Weibo Wang、Gerald B. Hammond、Bo Xu

  DOI：10.1021/ja3011397

  日期：2012.3.28

  Gold catalysis is considered one of the most important breakthroughs in organic synthesis during the past decade, but a rational understanding of ligand effects in gold catalysis is lacking. Most gold-catalyzed reactions go through three major stages: (i) electronic activation of alkyne (or allene) to generate a vinyl gold intermediate; (ii) protodeauration to generate the product and regenerate the

  金催化被认为是过去十年有机合成中最重要的突破之一，但缺乏对金催化中配体效应的合理理解。大多数金催化反应经历三个主要阶段：(i) 炔烃（或丙二烯）的电子活化以生成乙烯基金中间体；(ii) 原脱氢生成产物并再生阳离子金催化剂；(iii) 活性金催化剂的衰变。我们的研究让我们更清楚地了解配体如何影响金催化循环的三个阶段中的每一个阶段。更重要的是，通过不关注特定的金催化反应，我们已经能够对大多数金催化反应进行分类，并为每一类金催化反应提出配体设计方案。