Cu(bis(2,6-dimethylphenyl)penta-2,4-diiminato)(acetonitrile) | 467232-84-4

• 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: Cu(bis(2,6-dimethylphenyl)penta-2,4-diiminato)(acetonitrile)
• 英文别名: ([{N-(C₆H₃Me₂-2,6)C(Me)}₂CH]⁻Cu⁺)；(2,4-bis(2,6-dimethylphenylimido)pentyl)Cu(MeCN)；(CH(C(CH3)N(C6H3(CH3)2))2)Cu(acetonitrile)；Cu(N,N'-bis(2,6-Me2C6H3)nacnac)(CH3CN)；[(N(2,6-Me2C6H3)C(CH3))2CH]Cu(MeCN)
• CAS: 467232-84-4
• 化学式: C₂₃H₂₈CuN₃
• 分子量: 410.041
• InChiKey: DHCCPYODSVXQIA-RWDKFMNMSA-N

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：

  arsenic 、 Cu(bis(2,6-dimethylphenyl)penta-2,4-diiminato)(acetonitrile) 以 甲苯 为溶剂， 反应 0.67h， 以30%的产率得到
  参考文献：
  名称：

  Coordination of cage compounds by Cu(I) nacnac compounds

  摘要：

  The nacnac Cu(I) compound [L1Cu(MeCN)] (L1 = [{N(C6H3Me2-2,6)C(Me)}2CH]−) was reacted with E4 (P4, As4 and AsP3) yielding the homobimetallic complexes [(L1Cu)2(η2:2-E4)] (E4 = P4 (1a), As4 (1b), AsP3 (1c)) and the mononuclear complexes [L1Cu(η2-E4)] (E4 = P4 (2a), As4 (2b), AsP3 (2c)), revealing neutral, intact side-on coordinated E4 units. Furthermore, the reaction of [L1Cu(MeCN)] with Sered and E4S3

  DOI：

  10.1016/j.poly.2022.115957
• 作为产物：
  描述：

  甲苯 以 氘代苯 、 甲苯 为溶剂， 生成 Cu(bis(2,6-dimethylphenyl)penta-2,4-diiminato)(acetonitrile)
  参考文献：
  名称：

  Syntheses and structures of bis(2,6-xylyl-nacnac) copper(I) complexes

  摘要：

  The copper(I) complexes {(bis-2,6-dimethylphenyl-penta-2,3-diiminato)Cu}(2)(mu-toluene), 3 has been prepared and its reactivity against Lewis bases and nitrous oxide investigated. Complex 3 crystallizes as a toluene-bridged dimer and forms mono- and dinuclear benzene adducts in C6D6 solution. It does not coordinate excess THF, but reacts quantitatively with 1 equiv. of acetonitrile. Reaction with 2,6-xylyl isonitrile yields (bis-2,6-dimethylphenyl-penta-2,3-diiminato) Cu(2,6-xylyl isonitrile), 5, (nu(CN) = 2123 cm (1)), which was characterized by an X-ray diffraction study. Complex 3 does not react with nitrous oxide in either C6D6 solution (5 days 50 degrees C) or in diethyl ether (13 days at ambient temperature). (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2008.05.008

文献信息

• Copper Chemistry of β-Diketiminate Ligands:  Monomer/Dimer Equilibria and a New Class of Bis(μ-oxo)dicopper Compounds
  作者：Douglas J. E. Spencer、Anne M. Reynolds、Patrick L. Holland、Brian A. Jazdzewski、Carole Duboc-Toia、Laurent Le Pape、Seiji Yokota、Yoshimitsu Tachi、Shinobu Itoh、William B. Tolman

  DOI：10.1021/ic020369k

  日期：2002.12.1

  silence, diagnostic UV-vis absorption data, and O-isotope-sensitive resonance Raman spectroscopic features. The structural features of the compounds [LCuCl](2) and LCu(MeCN) as well as the proclivity to form bis(mu-oxo)dicopper products upon oxygenation of the Cu(I) complexes are compared to data previously reported for complexes of more sterically hindered beta-diketiminate ligands (Aboelella, N. W.;

  制备了一系列具有一系列取代模式的各种β-二酮基配体（L（-））的一系列Cu（I）和Cu（II）配合物，并通过光谱，电化学以及在某些情况下通过X-进行了表征射线晶体学方法。具体而言，对通式[LCuCl]（2）的配合物进行结构表征，并通过溶液的EPR光谱，以及在一种情况下，通过对粉末样品进行可变温度SQUID磁化测量，评估其磁性能。紫外可见光谱表明在高于-55摄氏度的温度下溶液中可逆解离为三配位单体LCuCl.Cu（I）络合物LCu（MeCN）表现出可逆性Cu（I）/ Cu（II）氧化还原对与E（1 / 2）相对于NHE（循环伏安法，MeCN溶液）的+300至+520 mV之间的值。这些配合物与O（2）具有高度反应性，产生的中间体根据其EPR沉默，诊断性UV-vis吸收数据和O-同位素敏感被确定为中性双（mu-oxo）双金属配合物的稀有实例共振拉曼光谱特征。将化合物[LCuCl]（2）和LCu
• Nitric Oxide Oxidatively Nitrosylates Ni(I) and Cu(I) <i>C</i>-Organonitroso Adducts
  作者：Stefan Wiese、Pooja Kapoor、Kamille D. Williams、Timothy H. Warren

  DOI：10.1021/ja903550n

  日期：2009.12.23

  equiv of ArNO to [Me(2)NN]Cu(NCMe). The X-ray structures of 3a and 3b are similar to those of related Cu(I) alkene adducts, with N-O distances in the narrow range 1.333(4)-1.338(5) A. IR spectra of the nitrosobenzene adducts 1b, 2b, and 3b exhibit nu(NO) stretching frequencies at 915, 1040, and 1113 cm(-1), respectively, following the decreasing degree of N=O activation observed in the X-ray structures

  一价镍和铜 β-二酮亚胺络合物与 ArN=O (Ar = 3,5-Me(2)C(6)H(3), Ph) 反应生成 C-亚硝基加合物，其表现出三种不同的键合模式NO 键活化的程度。将 ArNO 添加到 2 当量的 [Me(2)NN]Ni(2,4-二甲基吡啶) [Me(2)NN](-) = 2,4-双(2,6-二甲基苯基亚氨基)戊基} [Me(2)NN]Ni}(2)(mu-eta(2):eta(2)-ONAr)（1a 和 1b），在两个 [Me(2) )NN]Ni 碎片，1a 中的 NO 键距为 1.440(4) A，明显长于游离 C-有机亚硝基化合物 (1.13-1.29 A) 中的键距。[Me(2)NN]Cu(NCMe) 与 0.5 当量的 ArNO 在乙醚中反应生成双核加合物 [Me(2)NN]Cu}(2)(mu-eta(2):eta(1)- ONAr) (2a 和 2b)，其展示了
• Intermediates in Reactions of Copper(I) Complexes with <i>N</i>-Oxides: From the Formation of Stable Adducts to Oxo Transfer
  作者：Sungjun Hong、Aalo K. Gupta、William B. Tolman

  DOI：10.1021/ic900435p

  日期：2009.7.20

  Reactions of copper(I) complexes of bidentate N-donor supporting ligands with pyridine- and trimethylamine-N-oxides or PhIO were explored. Key results include the identification of novel copper(I) N-oxide adducts, aryl substituent hydroxylation, and bis(μ-oxo)dicopper complex formation via a route involving oxo transfer.

  研究了双齿 N 供体支持配体的铜 (I) 配合物与吡啶-和三甲胺-N-氧化物或 PhIO 的反应。主要结果包括新型铜 (I) N-氧化物加合物的鉴定、芳基取代基羟基化和双（μ-氧代）二铜配合物通过涉及氧代转移的路线形成。
• Dinuclear Copper Complexes Based on Parallel β-Diiminato Binding Sites and their Reactions with O₂: Evidence for a Cu−O−Cu Entity
  作者：Peter Haack、Christian Limberg、Kallol Ray、Beatrice Braun、Uwe Kuhlmann、Peter Hildebrandt、Christian Herwig

  DOI：10.1021/ic101249k

  日期：2011.3.21

  [Me2C6H3Xanthdim](Cu(L))2 (L = CH3CN, 1, PPh3, 2, and PMe3, 3) that proved to be stable and were fully characterized. Single crystal X-ray diffraction analyses performed for the three complexes showed that considerable steric crowding within the binding pockets of 2 leads to a very long Cu−Cu distance while the structures of 1 and 3 are relaxed. Compounds 2 and 3 are relatively robust toward air, whereas 1 is very

  关于系统β-二酮基亚胺基-Cu I / O 2的研究揭示了有价值的见解，这些见解可以就含铜的单核加氧酶的行为进行讨论。另一方面，自然界也采用双核Cu酶激活O 2。在这种背景下，研究了配体体系[ Me 2 C 6 H 3 Xanthdim] 2-包含两个平行的β-diiminato结合位点，该结合位点由x吨骨架连接，在diiminato单元上具有2,3-二甲基苯基残基，涉及其铜配位化学。二亚胺[ Me 2 C 6 H3 Xanthdim]H2在乙腈，PPh3和PMe3存在下用CuOtBu处理，得到相应的配合物[ Me 2 C 6 H 3 Xanthdim]（Cu（L））2（L = CH3CN ，1，PPH3，2，和PME3，3），其被证明是稳定的并充分表征。对这三种配合物进行的单晶X射线衍射分析表明，在2个结合口袋中有相当大的空间拥挤导致非常长的Cu-Cu距离，而1和3的结构则松弛。化合物2
• 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。