4-phenyl-1,5-bis-triphenylphosphinegold(I) 1,2,3-triazolate | 1325760-56-2

• 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: 4-phenyl-1,5-bis-triphenylphosphinegold(I) 1,2,3-triazolate
• 英文别名: 1-5-[PPh₃Au^I]₂(µ-N₃C₂-4-C₆H₅)；1-5-[PPh₃Au^I]₂(µ-1,2,3-triazolate-4-C₆H₅)；Ph(C2N3)(AuPPh3)2；5-phenyl-1,4-bis-triphenylphosphinegold(I) 1,2,3-triazolate
• CAS: 1325760-56-2；1325760-57-3
• 化学式: C₄₄H₃₅Au₂N₃P₂
• 分子量: 1061.66
• InChiKey: OKJLKHWWYNRUGR-UHFFFAOYSA-N

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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  phenylethynyl(triphenylphosphine)gold(I) 、 PPh₃Au^IC₈H₅ 以 氘代氯仿 为溶剂， 以100%的产率得到4-phenyl-1,5-bis-triphenylphosphinegold(I) 1,2,3-triazolate
  参考文献：
  名称：

  Au-iClick反映了铜催化的叠氮化物-炔烃环加成（CuAAC）的机理†

  摘要：

  本报告概述了金（I）-叠氮化物和金（I）-乙炔化物之间的iClick机理的研究，以产生三叠氮化物。digold三唑化物配合物的分离为CuAAC中两个铜（I）离子的作用提供了令人信服的支持。此外，动力学研究表明，该反应在Au（I）–N 3和Au（I）–C C–R中均为一级反应，因此总体上为二级反应。具有ρ的Hammett图= 1.02（5）表示吸电子基团通过促进π络合物中第二个金离子的配位来加速环加成反应。通过向反应中加入游离的三苯基膦来抑制速率，表明配体解离是反应的先决条件。机理结论与针对CuAAC反应提出的结论相似。

  DOI：

  10.1039/c5dt02405f

文献信息

• Excited-State Turn-On of Aurophilicity and Tunability of Relativistic Effects in a Series of Digold Triazolates Synthesized via iClick
  作者：Charles J. Zeman、Yu-Hsuan Shen、Jessica K. Heller、Khalil A. Abboud、Kirk S. Schanze、Adam S. Veige

  DOI：10.1021/jacs.0c01624

  日期：2020.5.6

  observed for aurophilic bonding. Though no bond exists in the ground state, time-dependent density functional theory interrogation of the complexes reveals excited states with significant aurophilic bonding. The series of complexes allows for tuning of the excited state "turn-on" of aurophilicity, where ligand to metal charge transfer (LMCT) induces the aurophilic bonding. Complexes containing lig-and localized

  Au(I) 炔化物 PPh3Au-C≡CR 之间的 iClick 反应，其中 R = 硝基苯基 (PhNO2)、苯基 (Ph)、噻吩 (Th)、联噻吩 (biTh) 和二甲基苯胺 (PhNMe2) 与 Au(I)-叠氮化物 PPh3AuN3提供通式R-1,5-双-三苯基膦金(I) 1,2,3-三唑盐(Au2-R)的二金配合物。在二金三唑盐配合物中，Au(I) 原子非常接近，但超出了亲金键合通常观察到的距离。尽管在基态中不存在键，但对复合物的时间相关密度泛函理论的询问揭示了具有显着亲热键合的激发态。该系列配合物允许调节亲热性的激发态“开启”，其中配体金属电荷转移 (LMCT) 诱导亲热键合。然而，含有 lig- 和局部激发态的复合物在激发态不表现出亲热性。作为对照实验，合成了单金配合物。计算出的单金物种的激发态在双核情况下表现出对金离子的 LMCT，但如果没有配对的金离子，只会发生明显的 N-Au-P
• 1,3-Dipolar cycloaddition between a metal–azide (Ph3PAuN3) and a metal–acetylide (Ph3PAuCCPh): an inorganic version of a click reaction
  作者：Trevor J. Del Castillo、Soumya Sarkar、Khalil A. Abboud、Adam S. Veige

  DOI：10.1039/c1dt10787a

  日期：——

  This report describes the synthesis and characterization of 1,5-bis-triphenylphosphinegold(I) 1,2,3-triazolate (3(1,5)). The synthesis of the dinuclear complex 3(1,5) is achieved via an unprecedented inorganic click (iClick) reaction between the metal–azide PPh3AuN3 (1) and the metal–acetylide PPh3Au–CCPh (2). Characterization of 3(1,5) includes multinuclear NMR spectroscopy, combustion analysis, and single crystal X-ray crystallography. Experimental characterization is complemented with density-functional-theory (DFT) calculations which indicate the 1,4-isomer 3(1,4) is less stable by 3.3 kcal mol−1. The energetic difference lies primarily in the ability of the phenyl group in the 4-position of 3(1,5) to lie coplanar with the triazolate to create a delocalized π-bonding HOMO orbital.

  本报告描述了1,5-双三苯基膦金(I)1,2,3-三唑(3(1,5))的合成和表征。二核络合物3(1,5)的合成是通过金属-叠氮化物PPh3AuN3(1)和金属-乙炔PPh3Au-CCPh(2)之间前所未有的无机点击(iClick)反应实现的。3(1,5)的表征包括多核核磁共振光谱、燃烧分析和单晶X射线晶体学。实验表征与密度泛函理论(DFT)计算相辅相成，后者表明1,4-异构体3(1,4)的稳定性降低了3.3 kcal MOl-1。这种能量差异主要在于3(1,5)中4位苯基与三唑共面，从而形成非局域Β键HOMO轨道。
• Inorganic click (iClick) synthesis of heterotrinuclear PtII/AuI2 complexes
  作者：Andrew R. Powers、Xi Yang、Trevor J. Del Castillo、Ion Ghiviriga、Khalil A. Abboud、Adam S. Veige

  DOI：10.1039/c3dt52105b

  日期：——

  Metal-azide–metal-acetylide cycloaddition (iClick) reactions to synthesize heterotrimetallics and an unexpected novel tetranuclear gold(I) complex, are described. In addition, a discussion regarding the connection between traditional azide–alkyne cycloaddition reactions and iClick is presented focusing on applications towards linking multiple metal ions.

  描述了用于合成异三金属和一种意想不到的新型四核金（I）配合物的金属-叠氮化物-金属-乙炔环加成（iClick）反应。此外，还讨论了传统叠氮-炔环加成反应与 iClick 之间的联系，重点关注连接多个金属离子的应用。
• Toward Permetalated Alkyne/Azide 3 + 2 or “Click” Cycloadducts
  作者：Melissa C. Clough、Paul D. Zeits、Nattamai Bhuvanesh、John A. Gladysz

  DOI：10.1021/om300542a

  日期：2012.8.13

  The Cu(I)-catalyzed reaction of the platinum butadiynyl complex trans-(C6F5)(p-tol(3)P)(2)Pt(C C)(2)H and rhenium cyclopentadienylazide complex (eta(5)-C5H4N3)Re(CO)(3) yields the 1,2,3-triazole trans-(C6F5)(p-tol(3)P)(2)PtC CC CHN(eta(5)-C5H4)Re(CO)(3))N N (54%), which upon treatment with Re-(CO)(5)OTf or Re(CO)(5)Br affords Re(CO)(5)+TfO- or cis-Re-(CO)(4)Br adducts derived from attack at N(3) (84-98%). The crystal structures of solvates of these three complexes are compared, but attempts to metalate the =CH groups were unsuccessful. However, the reaction of monometallic trans(C6F5)(p-tol(3)P)(2)PtC CC CHN(CH2C6H5)N=N and Mel gives an N(3)-methyl triazolium salt (81%), which upon addition of Ag2O and [RhCl(cod)](2) yields the N-heterocyclic carbene complex trans-(C6F5)(p-tol(3)P)(2)PtC CC-C(RhCl(cod))-N(CH2C6H5)-N-N(Me). Further experiments and analyses suggest that =CH derivatization is possible only when the H-1 NMR chemical shift is downfield of ca. delta 7.9 ppm. Electropositive metal fragments generally effect upfield shifts, meaning that insulating spacers, electronegative ligands, and/or new chemical methodologies will be required to construct tetrametallic arrays via click chemistry.
• [EN] METHOD FOR LINKING TWO OR MORE METALS FOR PHOTO AND ELECTRONIC MATERIALS<br/>[FR] PROCÉDÉ DE LIAISON D'AU MOINS DEUX MÉTAUX POUR MATÉRIAUX PHOTO ET ÉLECTRONIQUES
  申请人：UNIV FLORIDA

  公开号：WO2012058285A3

  公开（公告）日：2012-07-12