Au(SPh)(PPh3) | 14243-58-4

• 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: Au(SPh)(PPh3)
• 英文别名: benzenethiolato(triphenylphosphine)gold(I)；phenylthiolato(triphenyl)phosphinegold(I)；Au(SPh)(PPh₃)；Ph3PAuS(Ph)
• CAS: 14243-58-4
• 化学式: C₂₄H₂₀AuPS
• 分子量: 568.429
• InChiKey: UTIIDUGXLMYYKQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.69
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  Au(SPh)(PPh3) 、 4-硝基苯胺 在 三氟化硼乙醚 、 亚硝酸特丁酯 、 维生素 C 作用下， 以 甲醇 、 乙腈 为溶剂， 生成 4-硝基苯基苯硫
  参考文献：
  名称：

  金介导的芳基重氮盐与硫醇的 C−S 交叉偶联

  摘要：

  描述了金介导的芳基重氮盐与硫醇的 C−S 交叉偶联。该协议的相关性是使用容易获得且简单的金络合物 Me 2 SAuCl。该反应在温和的条件下进行，并且在重氮盐和硫醇中都有较宽的范围。

  DOI：

  10.1002/ejoc.202300203
• 作为产物：
  描述：

  三苯基膦氯金 、 三丁基(苯基硫基)锡烷 以 四氢呋喃 为溶剂， 以93%的产率得到Au(SPh)(PPh3)
  参考文献：
  名称：

  Synthesis, X-ray molecular structure analysis, and study on ligand scrambling reactions of new thiolatogold(I) complexes with various phosphines

  摘要：

  Treatment of Au(PPh3)Cl, (AuCl)(2)(trans-dpen) and (AuCl)(2)(dppfe) with Sn(SPh)(n-Bu)(3) and/or PhSH/KOH affords Au(PPh3)(SPh) (1), (AuSPh)(2)(mu -trans-dpen) (2), (AuSPh)2(mu -dppfe) (3), (AuSPh)(mu -trans-dpen)(AuCl) (4), and (AuSPh)-(mu -dppfe)(AuCl) (5) in good yields. All these thiophenolates are characterized by single crystal X-ray analysis, H-1 and P-31 NMR spectroscopy. 1 forms tetramer through Au . . . Au interaction and pi-pi interaction between the phenyl group in SPh and one of the phenyl groups in PPh3 in the solid state. An infinite chain structure is formed for 2 through intermolecular aurophilicity and these chains are connected by partial overlap (pi-pi interaction) of neighboring phenyl groups in SPh to give two-dimensional networks in the solid state. Similar infinite chains are formed through aurophilicity, but two-dimensional networks are not formed for 4 in the solid state. No multidimensional structure is formed for 3 and 5 in the solid state. H-1 and P-31 NMR spectroscopy of CDCl3 solutions of 2, 3, 4, and 5 has revealed that rapid ligand scrambling takes place for 4 and 5. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(00)00353-4

文献信息

• Aurolysis of α-C-deprotonated group 6 aminocarbene and thiocarbene complexes with Ph₃PAu⁺
  作者：Helgard G. Raubenheimer、Matthias W. Esterhuysen、Gernot Frenking、Alexey Y. Timoshkin、Catharine Esterhuysen、Ulrike E. I. Horvath

  DOI：10.1039/b607613k

  日期：——

  aminocarbene complexes, (CO)5M=C(NR2)CH3 (M = Cr or W; R = Me or propyl), react with Ph3PAu+ by metal group substitution - (CO)5M for Ph3PAu+--and attachment of the extricated M(CO)5 to the deprotonated methyl group. (The products may also be seen as aminovinylgold compounds coordinated to M(CO)5 moieties.) DFT calculations at the B3LYP level of theory using model compounds indicate a clear preference

  去质子化的Fischer型氨基碳烯配合物（CO）5M = C（NR2）CH3（M = Cr或W; R = Me或丙基），通过金属基团取代与Ph3PAu +反应-（CO）5M取代Ph3PAu +-并连接M（CO）5脱去质子化的甲基。（该产物还可以看作是与M（CO）5部分配位的氨基乙烯基金化合物。）使用模型化合物在B3LYP理论水平上进行DFT计算，表明中心单元C的金单元明显优先于配体[NMe2C ]-，而Cr（CO）5与N-配位相比具有7 kcal mol（-1）的C（乙烯基）配位偏好。在相关的硫代碳烯中，硫供体原子应该是羰基金属单元的优选连接点。后一种预测在实践中得到证实，在孤立的三种产品中，在与[Ph3PAuSPh] Cr（CO）5的混合晶体中包含Ph3PAu C（= CH2）SPh} Cr（CO）5时，恰好存在这种配位模式。混合晶体的后一种组分也已经独立于乙烯基化合物而制备。
• Gold–ruthenium compounds containing bridging phosphide or thiolate groups: Crystal structures of the intermediate species [Ru3(CO)8L(μ3-η2,η4,η3-{Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3})] (L=NMe3 or PPh2H)
  作者：Esther Delgado、Elisa Hernández、Miguel A. Maestro、Angel Nievas、Maria Villa

  DOI：10.1016/j.jorganchem.2006.05.008

  日期：2006.8

  New tetranuclear complexes have been prepared using bridging phosphide or thiolate groups between phosphine gold fragments and the compound [Ru3(CO)9(μ3-η2,η4,η3-Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3})]. The crystal structures of the intermediates [Ru3(CO)8(NMe3)(μ3-η2,η4,η3-Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3})] and [Ru3(CO)8(PPh2H)(μ3-η2,η4,η3-Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3})] have been solved.

  新的四核配合物已经使用桥接磷化物或膦金片段和化合物的[Ru之间硫醇基团制备3（CO）9（μ 3 -η 2，η 4，η 3 - 我3 SICC（C 2 Fc）的SC（ Fc）CSCCSiMe 3 }]。中间体的晶体结构的[Ru 3（CO）8（NME 3）（μ 3 -η 2，η 4，η 3 - 我3 SICC（C 2 Fc）的SC（FC）CSCCSiMe 3 }）]和[ Ru 3（CO）8（PPH 2 H）（μ 3 -η 2，η 4，η 3 - 我3 SICC（C 2的Fc SC（FC CSCCSiMe））3 }）]已被解决。
• Luminescence Studies of Gold(I) Thiolate Complexes
  作者：Jennifer M. Forward、David Bohmann、John P. Fackler、Richard J. Staples

  DOI：10.1021/ic00129a019

  日期：1995.12

  A series of monomeric gold(I) complexes containing phosphine and thiolate ligands have been synthesized. The two phosphines used were triphenylphosphine and the 1,3,5-triaza-7-phosphaadamantanetriylphosphine (TPA). Substituted benzenethiolate ligands were used with the substituent in either the ortho, meta or para position. All of the compounds synthesized luminesce at 77 K in the solid state, where the excitation is assigned to a ligand to metal charge transfer (LMCT) transition from the sulfur of the thiolate ligand to the gold center. The large Stokes shifts and long lifetimes measured imply that the emission is phosphorescence. The position of the emission maxima can be affected by both the substituents on the thiolate ligand and the presence of gold-gold interactions between neighboring molecules in the solid state. Four of these compounds have been structurally characterized. Compound 3 crystallizes in the triclinic space group P (l) over bar (No. 2) with cell constants a = 8.641(2) Angstrom, b = 11.423(2) Angstrom, c = 12.118(2) Angstrom, alpha = 103.36(3)degrees, beta = 99.34(3)degrees, gamma = 105.95(3)degrees, and Z = 2. Refinement of 2861 reflections and 253 parameters yields R = 0.0275 and R(w) = 0.0669. Compound 4 crystallizes in the orthorhombic space group P2(1)2(1)2(1) (No. 18) with cell constants a = 6.3100(10) Angstrom, b = 12.127(3) Angstrom, c 18.193(3) Angstrom, and Z = 4. Refinement of 1231 reflections and 163 parameters yields R = 0.0292 and R(w) = 0.0360. Compound 5 crystallizes in the monoclinic space group P2(1)/n (No. 13) with cell constants a = 12.252(3) Angstrom, b = 17.002(6) Angstrom, c = 22.845(4) Angstrom, beta = 91.25(2)degrees and Z = 12. Refinement of 5534 reflections and 541 parameters yields R = 0.0698 and R(w) = 0.0786. Compound 10 crystallizes in the monoclinic space group C2/c (No. 15) with cell constants a = 17.542(5) Angstrom, b = 18.831(6) Angstrom, c = 11.647(4) Angstrom, beta = 119.52(2)degrees, and Z = 8, Refinement of 2207 reflections and 181 parameters yields R = 0.0327 and R(w) = 0.0441.
• Nakamoto, Masami; Hiller, Wolfgang; Schmidbaur, Hubert, Chemische Berichte, 1993, vol. 126, # 3, p. 605 - 610
  作者：Nakamoto, Masami、Hiller, Wolfgang、Schmidbaur, Hubert

  DOI：——

  日期：——
• Regioselective Cis Insertion of DMAD into Au–P Bonds: Effect of Auxiliary Ligands on the Reaction Mechanism
  作者：Hitoshi Kuniyasu、Takuya Nakajima、Takashi Tamaki、Takanori Iwasaki、Nobuaki Kambe

  DOI：10.1021/acs.organomet.5b00078

  日期：2015.4.13

  The cis insertion of dimethyl acetylenedicarboxylate (DMAD, 2) into the Au-P bond of Au(SAr)(PAr'3) (1) occurs selectively at room temperature to give adduct 3, whose X-ray crystallographic analysis exhibits the predominant character of an alkenylphosphorus zwitterion complex. The first-order kinetics with respect to 1 and 2 and the large negative value of Delta S-double dagger indicate that the reaction proceeds through the coordination of 2 to 1 followed by a concerted inner-sphere nucleophilic attack of PPh3 on the coordinated triple bond. In contrast, Au(Cl)(PPh3) (4) does not react with 2 even at 60 degrees C. However, the tricoordinated 16-electron complex Au(Cl)(PPh3)(2) (5) quite successfully reacts with 2 to produce insertion product 6, demonstrating that two PPh3 ligands are required for the reaction.