(methyl isonitrile)gold(I) chloride | 37131-30-9

• 英文名称: (methyl isonitrile)gold(I) chloride
• 英文别名: methylisonitrile gold(I) chloride；chloro(methylisocyanide)gold；(methyl isocyanide)AuCl；MeNCAuCl
• CAS: 37131-30-9
• 化学式: C₂H₃AuClN
• 分子量: 273.472
• InChiKey: ZAYJMGPULXMHNM-UHFFFAOYSA-M

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：

  (methyl isonitrile)gold(I) chloride 以 neat (no solvent) 为溶剂， 生成 金
  参考文献：
  名称：

  Gold(i)–isocyanide and gold(i)–carbene complexes as substrates for the laser decoration of gold onto ceramic surfaces

  摘要：

  我们制备了异氰酸金络合物 XAu(RNC)（X = 卤化物、假卤化物，R = 烷基、芳基）和水溶性羰基金络合物 XAuC(NHPh)[MeN(CH2CH2O)nMe] （X = Cl，n = 1â11），并对其进行了评估，将其作为在陶瓷上直接激光写金装饰的基底。

  DOI：

  10.1039/b617347k
• 作为产物：
  描述：

  (tetrahydrothiophene)gold(I) chloride 、 甲胩 以 二氯甲烷 为溶剂， 生成 (methyl isonitrile)gold(I) chloride
  参考文献：
  名称：

  具有扩展的亲和性超分子结构的中性金（I）有机金属配合物的光物理和键合。

  摘要：

  这项工作代表了在溶液和固态中Au（CO）Cl中分子光谱和键合的协同实验/计算研究。对于Au（CO）Cl和相关的（RNC）AuCl络合物，它们同样堆积在无限链中，结晶固体的发光行为相似，并且都显示出橘红色的非结构化磷光带，斯托克斯位移非常大（（15-20）×10 3厘米-1）。为基态计算的长亲离距离（约3.2Å）在磷光激发态（约2.6Å）中收缩，表明了赋形体Au-Au共价键。光谱数据表明磷光物质中的激基Au-Au键延伸到固态附近的两个相邻分子之外。由于二聚体物质的发射能量（在蓝色区域中）比结晶固体的发射能量高，并且通过从头算来得到再现，因此控制冷冻溶液中的浓度可获得磷光带。本文的光谱发现表明，可以通过发光行为获得关于超分子结构的预测信息。以（1,1,3,3-Me 4的晶体为例BuNC）AuCl，其橘红色的发光预期具有延长链的超分子结构，该结构后来通过晶体学验证，因为发现分子排列成锯齿形链，亲金距离短（3

  DOI：

  10.1021/om060524t

文献信息

• Structural Investigation of Bis(isonitrile)gold(I) Complexes
  作者：Wolfgang Schneider、Alexander Sladek、Andreas Bauer、Klaus Angermaier、Hubert Schmidbaur

  DOI：10.1515/znb-1997-0110

  日期：1997.1.1

  The reaction of (MeNC)-, (PhNC)- and (MesNC)AuCl in tetrahydrofuran with an equimolar amount of the corresponding isonitrile ligand and one equivalent of Ag⁺X^- (X^-= BF^- ₄ or CF₃SO^- ₃) leads to the formation of the bis(isonitrile)gold(I) complexes (MeNC)₂Au⁺ CF₃SO^- ₃(1), (PhNC)₂Au⁺ BF^- ₄ (2) and (MesNC)₂Au⁺ BF^- ₄(3). The crystal structures of 1, 2 and 3 have been determined. In compound 1 there are rod-like cations with a parallel packing into meandering puckered layers, in which the gold atoms have alternating Au-Au contacts of 3.611 and 3.624 Å. In complex 2 the cations form long double-paddles, with the two paddles at an angle of 77.5°. The individual cations are well separated and have no sub-van-der-Waals Au-Au contacts. The crystal structure of 3 is similar, but with a smaller dihedral angle between the planes of the two mesityl rings (56.0°)

  (MeNC)-、(PhNC)-和(MesNC)AuCl在四氢呋喃中与相应的异腈配体的等摩尔量和一当量的Ag^+X^- (X^-= BF^-4或CF3SO3-) 反应，形成双(异腈)金(I)配合物(MeNC)2Au^+ CF3SO3-3(1)、(PhNC)2Au^+ BF^-4(2)和(MesNC)2Au^+ BF^-4(3)。已确定了1、2和3的晶体结构。在化合物1中，有棒状阳离子平行堆积成蜿蜒起伏的层，金原子之间交替的Au-Au接触为3.611和3.624 Å。在复合物2中，阳离子形成长双桨，两个桨之间的夹角为77.5°。单个阳离子之间相互分离，没有亚-范德瓦尔斯Au-Au接触。化合物3的晶体结构类似，但两个二甲苯环的平面之间的二面角较小(56.0°)。
• Ligand Influences on the Supramolecular Chemistry of Simple Gold(I) Complexes: Mononuclear (Isonitrile)gold(I) Complexes
  作者：Wolfgang Schneider、Klaus Angermaier、Alexander Sladek、Hubert Schmidbaur

  DOI：10.1515/znb-1996-0606

  日期：1996.6.1

  A series of (isonitrile)gold(I) complexes has been synthesized: (MeNC)AuX (X = Cl la, I lc), (t-BuNC)AuBr 2b. (PhNC)AuX (X = Cl 3a. Br 3b. I 3c. SCN 3d), (MesNC)AuCl 4a [mes=mesityl], and (MeOC(O)CH₂NC)AuX (X = Cl 5a. Br 5b. I 5c. SCN 5d). The chlorides were prepared by the reaction of (Me₂S)AuCl with equimolar amounts (or with an excess) of the corresponding isonitrile. The bromides, iodides and thiocyanates were obtained from the reaction of (RNC)AuCl with K⁺X^- (X = Br, I, SCN) in the two-phase system H₂O/CH₂CI₂. The molecular and crystal structures of la. 2b. 3a-c, 4a, and 5a-c have been determined by X-ray diffraction methods. In the solid state the molecules are aggregated through short Au-Au contacts into dimers (4a and 5c), chains (la, 2b and 3a-c) or sheets (5a and 5b). The influence of the isonitrile and halide ligands on the type and strength of the intermolecular Au-A u contacts is discussed

  合成了一系列（异腈）金（I）配合物：（MeNC）AuX（X = Cl la，I lc），（t-BuNC）AuBr 2b，（PhNC）AuX（X = Cl 3a，Br 3b，I 3c，SCN 3d），（MesNC）AuCl 4a [mes = 甲基丙烯酸甲酯基] 和（MeOC（O）CH2NC）AuX（X = Cl 5a，Br 5b，I 5c，SCN 5d）。氯化物是通过（Me2S）AuCl与相应的异腈的等摩尔量（或过量）反应制备的。溴化物、碘化物和硫氰酸盐是从（RNC）AuCl与K+X-（X = Br，I，SCN）在两相系统H2O / CH2CI2中反应得到的。la，2b，3a-c，4a和5a-c的分子和晶体结构已通过X射线衍射法确定。在固态中，分子通过短的Au-Au接触聚集成二聚体（4a和5c），链（la，2b和3a-c）或片（5a和5b）。讨论了异腈和卤化物配体对分子间Au-Au接触类型和强度的影响。

• 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.
• Amin-Additionen an μ-(1,2-Diisocyanobenzol)-bis(chlorogold): Reaktionsbeteiligung der Isocyan-Nachbarfunktion und [Au]C-Übertragung
  作者：Wolf Peter Fehlhammer、Wilhelm Finck

  DOI：10.1016/0022-328x(91)86106-z

  日期：1991.8

  mu-(1,2-Diisocyanobenzene)bis(chlorogold) (2) reacts with 1,2-diaminobenzene (1/1) to give benzimidazolin-2-ylidene(chloro)gold (3) as the only reaction product, while 1/1-mixtures of 3 and the corresponding diaminocarbene complexes (4, 6) result from the reactions of 2 with 1,8-diaminonaphthalene or two equivalents of aniline. With one equivalent of a primary amine (MeNH2, PhNH2), however, the isocyanide complexes Au(Cl)CNR (R = Me, Ph) are obtained, again together with 3. Mechanistic key steps following the primary nucleophilic attack by the amine are a novel NC-coupling of the two neighbouring isocyano functions to give a benzimidazole ring system, and the transfer of the exocyclic Au(Cl)C fragment onto the incoming amine. Accordingly, the reactions between 2 and secondary amines lead to an isolable binuclear intermediate C' (1/1) or to the carbene complexes Au(Cl)C(NR2)2} (8, 2R = (CH2)5; 9, 2R = (CH2)2O(CH2)2; 10, R = Me; 11, 2R = (CH2)4) (1/2), respectively.7 and morpholine give 3 and the asymmetrical diaminocarbene complex Au(Cl)C[ activated N(CH2)4CH2]-[ activated N(CH2)2OCH2CH2]} (12).