[AuCl3(CNBut)] | 953400-52-7

• 英文名称: [AuCl3(CNBut)]
• 英文别名: [AuCl₃(CNBu^t)]
• CAS: 953400-52-7
• 化学式: C₅H₉AuCl₃N
• 分子量: 386.459
• InChiKey: OQBAFWQRPHXXHK-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 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：

  [AuCl3(CNBut)] 、 N-methyl-4-tolylnitrone 以 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  硝基的1,3-偶极环加成反应与金（III）结合的异氰酸酯

  摘要：

  Treatment of gold(III)-isocyanides [AuCl3(CNR1)] (R-1 = Xyl 1, Cy 2, Bu-t 3) with an equimolar amount of 5,5-dimethyl-1-pyrroline-N-oxide (4) in CH2Cl2 at -74 degrees C leads to the generation of the heterocyclic aminocarbene species [AuCl3{C((ONCMe2CH2CH2CH)-C-a-H-b)-NeR1}(N-a-C-b)(C-b-N-e)] 8 (for R-1 = Bu-t) or gold(III) complexes cis-[AuCl2{N-a((CMe2CH2CH2CNR1)-N-b-R-e)C-d= O}(N-a-C-b)(N-e-C-d)] 9 and 10 (for R-1 = Xyl and Cy) in good isolated yields (75-87%). DFT calculations show that deprotonation of the endocyclic CH group in the carbene ligand leads to spontaneous N-O bond cleavage, and acidity of this group is a factor controlling the different chemical behavior of 1-3 depending on the nature of substituent R-1. The reaction of equimolar amounts of the aldonitrone p-TolCH=N+(Me)O- (5) or the ketonitrones Ph2C=N+(R-2)O- (R-2 = Ph 6, CH2Ph 7) with 1-3 in CD2Cl2 at -70 degrees C in air (or under N-2) revealed the formation of the carbene complexes [AuCl3{C(ONMeCaH-p-Tol)-(NR1)-R-b}(C-a-N-b)] (R-1 = Cy 11, Xyl 12, Bu-t 13), [AuCl3{C(ONPhCaPh2)-(NR1)-R-b}(C-a-N-b)] (R-1 = Cy 14, Bu-t 15), or [AuCl3{C(ON(CH2Ph)CaPh2)-(NR1)-R-b}(C-a-N-b)] (R-1 = Cy 16, Xyl 17), as studied by H-1 NMR. The reaction of 6 with 1 and of 7 with 3 did not furnish carbene products. Compounds 8-10 were characterized by ESI-MS, IR, 1D (H-1, C-13{H}) and 2D (H-1,H-1-COSY, H-1,C-13-HSQC, H-1,C-13-HMBC) NMR spectroscopic techniques, and, only for 8, elemental analyses (C, H, N), while compounds 11-17 were characterized by D-1 (H-1, C-13{H}) and 2D (H-1,C-13-HSQC) NMR. Structures of compounds 8, 9, and 13 were additionally established by single-crystal X-ray diffraction.

  DOI：

  10.1021/acs.organomet.6b00635
• 作为产物：
  描述：

  (t-butylisocyanide)gold(I) chloride 、 氯 以 二氯甲烷 为溶剂， 反应 0.01h， 以96%的产率得到[AuCl3(CNBut)]
  参考文献：
  名称：

  将N-亲核试剂加到与金（iii）结合的异氰化物上，导致金（iii）短环无环二氨基卡宾络合物的寿命短†

  摘要：

  [AuCl 3（CNR 1）]（R 1 = Xyl，Cy，（S）-CHMePh）与胺的反应意外地通过氧化还原途径进行，从而生成金（I）-异氰化物和亚胺，同时在苯甲酮中添加了二苯甲酮。室温下[AuCl 3（CNR 1）]中的异氰酸酯配体导致金（III）无环二氨基卡宾络合物[AuCl 3 {C（NHNCPh 2）NHR 1 ]]寿命短。

  DOI：

  10.1039/c7nj00529f

文献信息

• Tetrazol-5-ylidene Gold(III) Complexes from Sequential [2 + 3] Cycloaddition of Azide to Metal-Bound Isocyanides and N4 Alkylation
  作者：Mikhail A. Kinzhalov、Alina S. Legkodukh、Tatyana B. Anisimova、Alexander S. Novikov、Vitalii V. Suslonov、Konstantin V. Luzyanin、Vadim Yu. Kukushkin

  DOI：10.1021/acs.organomet.7b00591

  日期：2017.10.23

  analyses (C, H, N), HRESI–-MS, FTIR, and 1H and 13C1H} NMR spectroscopies. Complexes 5a–d were obtained as colorless solids and characterized by elemental analyses (C, H, N), HRESI+-MS, and 1D (1H and 13C1H}) and 2D (1H,13C-HMBC) NMR spectroscopies. In addition, the structures of 3a, 3b, 3c, and 5a were established by single-crystal X-ray diffraction. Analysis of the Wiberg bond indices (WI) for

  等摩尔量的异氰酸酯络合物[AuCl 3（C NR）]之间的反应[R = 2,6-Me 2 C 6 H 3（Xyl），1a ; 2,4,6-Me 3 C 6 H 2（Mes），1b ; Cy，1c ; 室温下，t- Bu，1d和叠氮化四丁基铵（2）在CH 2 Cl 2中进行约10分钟，得到四唑酸金（III）[ n -Bu 4 N] [AuCl 3（C N 4 R）]。 （3a – d），纯化后以89–95％的产率获得。等摩尔量的3a - d与三氟甲磺酸甲酯（MeOTf）之间的后续反应在CH 2 Cl 2中于-70°C进行约30分钟，得到相应的金（III）络合物[AuCl 3（C a N（Me）N 2 N b R）] a–b（5a – d）带有1,4-二取代的四唑-5-亚烷基配体（69–75％）。配合物3a – d为淡黄色固体，并通过元素分析（C，H，N），HRESI –-MS，FTIR和1 H和13
• Photochemistry of Neutral Isonitrile Gold(I) Complexes:  Modulation of Photoreactivity by Aurophilicity and π-Acceptance Ability
  作者：Oussama Elbjeirami、Mohammad A. Omary

  DOI：10.1021/ja0703933

  日期：2007.9.1

  This work demonstrates for the first time that aurophilicity and ligand pi-acceptance ability sensitize the photoreactivity of Au(I) complexes. Photolysis of (LAuCI)-C-1 (L = RNC or CO) complexes leads to free L, Au-III, and Au-0 photoproducts. Solutions of (p-tosyl)CH2NCAuCl in clichloromethane undergo significant oligomerization leading to dimers and trimers with formation constants of 1.61 x 10(3) and 6.61 X 10(3) M-1, respectively, representing the highest values reported to date for complexes that exhibit aurophilic association in solution. The photoproduct quantum yield Phi varies with the (LAuCl)-Cl-I concentration in solution. For (ptosyl)CH2NCAuCl, metallic gold forms with Phi = 0.0065 and 0.032 in 4.0 x 10(-5) and 4.0 x 10(-3) M dichloromethane solutions, respectively. Meanwhile, irradiation of t-BuNCAuCl primarily produces t-BuNCAuCl3 with Phi = 0.0045 and 0.013 for 5.0 x 10(-5) and 5.0 x 10(-3) M dichloromethane solutions, respectively. For Au(CO)Cl, metallic gold forms with Phi = 0.013 and 0.065 upon irradiation of 8.0 x 10(-5) and 8.0 x 10(-3) M clichloromethane solutions, respectively. Hence, *[LAuX](n) oligomeric species are more photoreactive than monomeric species. The results also demonstrate intuitive control of Phi via modulation of the pi-acceptance ability of L, as both follow CO > (p-tosyl)CH2NC > (alkyl)NC in LAuCl, a trend that is also commensurate with the relative long-term photosensitivity of the corresponding solids and solutions. A new method for preparing stable small gold nanoparticles is described based on the fundamental findings above. Thus, photolysis of different concentrations of LAuX in solutions containing a primary amineterminated dendrimer leads to clear solutions exhibiting tunable visible plasmon absorptions of gold nanoparticles; these solutions maintain their colors and stability indefinitely. TEM measurements for representative samples prepared by photolysis of (p-tosyl)CH2NCAuCl solutions give rise to spherical nanoparticles as small as 5 nm.