荚基化铜 | 75732-01-3

• 物质功能分类: 化学试剂 - 有机试剂 - 烯烃（环状与无环状）
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 荚基化铜
• 中文别名: 甲基异丁烯铜；2,4,6-三甲基苯铜
• 英文名称: mesitylcopper(I)
• 英文别名: mesityl copper (I) pentamer；[CuMes]₅；[Cu(2,4,6-trimethylphenyl)]₅；Cu₅Mes₅；copper(I) mesitylene；Cu5(2,4,6-Me3C6H2)5；copper(I) mesityl；[(Cu(mesityl))5]；mesitylcopper；Copper(1+) 2,4,6-trimethylbenzen-1-ide；copper(1+);1,3,5-trimethylbenzene-6-ide
• CAS: 75732-01-3
• 化学式: 5C₉H₁₁*5Cu
• 分子量: 913.662
• InChiKey: TYIFJJCPKPPNPM-UHFFFAOYSA-N

物化性质

• 熔点：
  184-191°C

计算性质

• 辛醇/水分配系数(LogP)：
  2.41
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• WGK Germany：
  3
• 危险性防范说明：
  P261,P264,P271,P280,P302+P352,P304+P340+P312,P305+P351+P338,P332+P313,P337+P313
• 危险性描述：
  H315,H319,H335

反应信息

• 作为反应物：
  描述：

  荚基化铜 在 氢气 作用下， 以 1,2,5-trimethyl-benzene 为溶剂， 生成 铜
  参考文献：
  名称：

  Organometallic Access to Intermetallic θ ‐CuE ₂ (E = Al, Ga) and Cu _{1– x} Al _x Phases

  摘要：

  AbstractIn this work, we compare different precursor approaches for the mild decomposition to copper–aluminum and –gallium powder materials in nonaqueous solution. Referring to previous work on the preparation of Cu–Al alloy materials from [(AlCp*)4] and [CpCu(PMe3)], the amine‐stabilized metal trihydrides [(Me3N)AlH3] and [(quinuclidine)GaH3] were used as alternative sources for Al and Ga. In a comparative study, [(Me3N)AlH3] and [(AlCp*)4] were treated with the Cu precursors [CpCu(PMe3)] and [{Cu(mesityl)}5] in mesitylene solution in various molar ratios at 150 °C and 3 bar H2 to give metallic precipitates of the composition Cu1–xAlx (x = 0.67, 0.50, 0.31). Whereas the combination [(AlCp*)4] with [{Cu(mesityl)}5] did not yield an intermetallic phase, all other Cu/Al precursor combinations led to alloyed Cu–Al materials. For x = 0.67, the θ‐CuAl2 phase formed, as shown by X‐ray powder diffraction (XRD) and solid‐state magic‐angle‐spinning (MAS)NMR spectroscopic studies. Similarly, the reaction of [{Cu(mesityl)}5] with [(quinuclidine)GaH3] immediately led to the precipitation of a gray powder, without the addition of hydrogen. The powder was identified by means of XRD as θ‐CuGa2. At x = 0.50 and below, the reactions were less phase selective depending on the precursor combination. [CpCu(PMe3)] combined with both Al precursors afforded a mixture of several Cu–Al phases, whereas [{Cu(mesityl)}5] was treated with [(Me3N)AlH3] to yield a material whose X‐ray signature was assigned to the monoclinic Cu0.51Al0.49 phase. The γ‐Cu9Al4 phase could not be obtained from [CpCu(PMe3)]; instead, solid solutions of α‐Cu were obtained. The treatment of [{Cu(mesityl)}5] with [(Me3N)AlH3] in the Cu/Al molar ratio of 9:4 (x = 0.31) gave a gray powder, which could be identified by XRD as γ‐Cu9Al4.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  DOI：

  10.1002/ejic.200800046
• 作为产物：
  描述：

  copper(l) chloride 、 magnesium,1,3,5-trimethylbenzene-6-ide,bromide 以 四氢呋喃 为溶剂， 以65%的产率得到荚基化铜
  参考文献：
  名称：

  Synthesis and thermal decomposition of copper(I) silyloxide complexes. X-ray crystal structures of [Cu(OSiPh3)]4 and [Cu(OSiPh3)(PMe2Ph)]2

  摘要：

  Homoleptic copper(I) silyloxide complexes [Cu(OSiR3)]4 [SiR3 = SiPh3 (2), SiPh3.toluene (1) SiMe2But(3), SiEt3 (4)] were prepared by reaction of copper(I) mesityl with equivalent amounts of silanol. Reaction of [Cu(OSiR3)]4 with phosphine donors gave adduct complexes featuring lower aggregation numbers: [Cu(OSiPh3)(PEt3)]2 (5), [Cu(OSiPh3) (PMe2Ph)]2 (6); [Cu(OSiMC2But)(PPh3)2] (7). No reaction was observed between [Cu(O SiPh3)]4.toluene and either sulphur donors (1,3,5-trithiane) or hard Lewis donors (THF, TMEDA). Potassium-sequestered complexes, [K(crown)][Cu(OSiPh3)2].1/2 toluene (8) and [K(crown)][Cu(OSiMe2But)2] (9), were prepared by reaction of [Cu(OSiR3]4, with equivalent amounts of [K(crown)][OSiR3]. The following complexes were characterized by single-crystal X-ray diffraction: [Cu(OSiPh3)]4 (2): a tetramer featuring: (1) linear copper centres linked by bridging -OSiPh3 ligands; (2) a planar Cu4O4 core with a crystallographically-imposed centre of inversion; and (3) no Cu-Cu or Cu-C bonding interactions. [Cu(OSiPh3)(PMe2Ph)]2 (6): a dimer featuring: (1) trigonal planar copper centres linked by bridging -OSiPh3 groups; (2) a planar Cu2O2P2 core with a crystallographically-imposed centre of inversion; and (3) unsymmetrical -OSiPh3 bridging between copper centres with Cu-O distances differing by 0.1 angstrom. The thermal decomposition of the [Cu(O SiR3)]4 series was investigated through bulk thermolysis studies, thermal gravimetric analysis and differential scanning calorimetry. Decomposition pathways involved Cu-O bond homolysis leading to elemental copper.

  DOI：

  10.1016/s0277-5387(00)83565-2

文献信息

• From elusive thio- and selenosilanoic acids to copper(i) complexes with intermolecular SiE → Cu–O–Si coordination modes (E = S, Se)
  作者：Gengwen Tan、Yun Xiong、Shigeyoshi Inoue、Stephan Enthaler、Burgert Blom、Jan D. Epping、Matthias Driess

  DOI：10.1039/c3cc41965g

  日期：——

  LSi(=Se)OH(dmap) 3 (L = CH[C(Me)NAr]2, Ar = 2,6-iPr2C6H3, dmap = 4-dimethylaminopyridine), the heavier analogue of the thiosilanoic acid adduct LSi(=S)OH(dmap) 1, is reported. Both adducts 1 and 3 react readily with MesCu (Mes = 2,4,6-trimethylphenyl) to form the novel dimeric Cu(I) complexes [LSi(=E)OCu]2 (4: E = S; 5: E = Se) with unprecedented intermolecular Si=E --> Cu-O-Si coordination modes. The latter

  第一种稳定的硒代硅铝酸基加合物LSi（= Se）OH（dmap）3（L = CH [C（Me）NAr] 2，Ar = 2,6-iPr2C6H3，dmap = 4-二甲基氨基吡啶）的合成据报道，硫代硅酸加合物LSi（= S）OH（dmap）1的重类似物。加合物1和3都容易与MesCu（Mes = 2,4,6-三甲基苯基）反应形成新颖的二聚Cu（I）络合物[LSi（= E）OCu] 2（4：E = S; 5：E = （Se）具有前所未有的分子间Si = E-> Cu-O-Si配位模式。后者是用于Cu（I）介导的苯乙烯与PhI = N（Ts）（Ts =甲苯磺酰基）的叠氮化的有效预催化剂。
• Copper‐Catalysed Electrophilic Amination of Aryl(alkenyl) Boronic Acids with Nitrogen‐Containing Hypervalent Iodine (III) Reagent
  作者：Yuanyuan Hu、Songlin Zheng、Wu Fan、Weiming Yuan

  DOI：10.1002/adsc.202100594

  日期：2021.10.19

  A copper-catalysed electrophilic N-imination of aryl(alkenyl) boronic acids with a stable hypervalent iodine(III) reagent containing a transferable (diarylmethylene)amino group is developed. The electrophilic C−N cross-coupling reaction proceeds smoothly at room temperature under oxidant-free and base-free conditions, which is further characterized by the broad functional group compatibility, thereof

  开发了一种铜催化的芳基（烯基）硼酸的亲电N-亚胺化反应，该反应使用含有可转移（二芳基亚甲基）氨基的稳定高价碘 (III) 试剂。亲电C-N的交叉偶联反应在室温下顺利地进行氧化剂-自由和无碱基的条件下，其特征还在于由广泛的官能团的相容性下，其延伸的Ñ -electrophile亲电C-N交的范围在N -O 和N -Cl 试剂限制之外进行偶联。
• A new class of organocopper and organocuprate compounds derived from copper(I) arenethiolates
  作者：D. Martin Knotter、David M. Grove、Wilberth J. J. Smeets、Anthony L. Spek、Gerard Van Koten

  DOI：10.1021/ja00035a036

  日期：1992.4

  Organometallic reagents (ZR; Z=Li, Mg, or Cu; R=Me, CH 2 SiMe 3 , or C 6 H 2 Me 3 -2,4,6) react with copper arenethiolates ([CuSAr] 3 ; SAr=SC 6 H 3 (CH(R')NMe 2 )-2-R''-3 (1, R'=R''=H; 2, R'=Me and R''=H (R-configuration); 3, R'=H and R«=Cl) to give well defined neutral species that have been isolated and characterized both in solution (mol wt determination by cryoscopy and microwave titration, both

  有机金属试剂（ZR；Z=Li、Mg 或 Cu；R=Me、CH 2 SiMe 3 或 C 6 H 2 Me 3 -2,4,6）与芳烃硫醇铜（[CuSAr] 3 ；SAr=SC 6 H 3 (CH(R')NMe 2 )-2-R''-3 (1，R'＝R''＝H；2，R'＝Me且R''＝H(R-构型)； 3, R'=H 和 R«=Cl) 得到明确定义的中性物质，这些物质已在溶液（通过低温和微波滴定法测定摩尔重量，在苯和 1 H NMR 中）和固体中分离和表征X射线晶体学状态
• Effects of Electron-Deficient β-Diketiminate and Formazan Supporting Ligands on Copper(I)-Mediated Dioxygen Activation
  作者：Sungjun Hong、Lyndal M. R. Hill、Aalo K. Gupta、Benjamin D. Naab、Joe B. Gilroy、Robin G. Hicks、Christopher J. Cramer、William B. Tolman

  DOI：10.1021/ic9002466

  日期：2009.5.18

  Copper(I) complexes of a diketiminate featuring CF3 groups on the backbone and dimethylphenyl substituents (4) and a nitroformazan (5) were synthesized and shown by spectroscopy, X-ray crystallography, cyclic voltammetry, and theory to contain copper(I) sites electron-deficient relative to those supported by previously studied diketiminate complexes comprising alkyl or aryl backbone substituents. Despite

  合成了主链上具有 CF 3基团和二甲基苯基取代基 ( 4 ) 和硝基甲 ( 5 )的二酮亚胺的铜 (I) 配合物，并通过光谱学、X 射线晶体学、循环伏安法和包含铜 (I) 的理论显示相对于先前研究的包含烷基或芳基骨架取代基的二酮亚胺配合物支持的那些位点缺电子。尽管 LCu(CH 3 CN) (L = 4或5) 在室温下产生双（羟基）二铜（II）化合物，在 -80 °C 下产生双（μ-氧代）二铜配合物，这些配合物基于紫外-可见光和共振拉曼光谱、分光光度滴定结果（2： 1 Cu/O 2比率）、电子顺磁共振波谱（无声）和密度泛函理论计算。由5支持的双（μ-氧代）二铜配合物表现出不寻常的光谱特性，并通过一种新的中间体衰变，该中间体被认为是金属拉维达基自由基配合物，这一发现突出了甲臜配体表现出“非无辜”行为的潜力。
• Reactivity studies of group 15 Zintl ions towards homoleptic post-transition metal organometallics: a ‘bottom-up’ approach to bimetallic molecular clusters
  作者：Caroline Knapp、Binbin Zhou、Mark S. Denning、Nicholas H. Rees、Jose M. Goicoechea

  DOI：10.1039/b911544g

  日期：——

  Reactions between ethylenediamine (en) solutions of the intermetallic Zintl phases K3E7 (E = P, As) and a series of homoleptic post-transition metal organometallics such as Cu5(Mes)5, M(C6H5)2 (M = Zn, Cd) and In(C6H5)3 have yielded a family of novel bimetallic cluster anions. These new species were isolated as [K(2, 2,2-crypt)]+ salts in [K(2,2,2-crypt)]4Cu2E14 (E = P (1), As (2)), [K(2,2,2-crypt)]4ZnE14

  之间的反应 乙二胺 （恩）金属间化合物Zintl相K 3 E 7（E = P，As）和一系列均相后过渡金属有机金属化合物，例如 铜5（Mes）5，M（C 6 H 5）2（M =锌，Cd）和In（C 6 H 5）3已产生一族新型双金属簇阴离子。这些新物种被分离为[K（2， 2,2-crypt）] +[K（2,2,2-crypt）] 4 Cu 2 E 14（E = P（1），As（2）），[K（2,2,2-crypt）] 4 ZnE 14（E = P（3），作为（4）），[K（2,2,2-crypt）] 4 CdP 14 ·6py（5）和[K（2,2,2-crypt）] 2 E 7 InPh 2（E = P（6），如（7））。种2，3，5和6进行了晶体学表征通过单晶X射线衍射。通过电喷雾质谱和1 H证实了溶液中所有簇状阴离子的稳定性。13 C 1 H} 和 31 P 1 H} NMR光谱法（如果可能）。