tetrakis(benzonitrile)copper(I) perchlorate | 15170-22-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tetrakis(benzonitrile)copper(I) perchlorate
• 英文别名: copper(I) perchlorate tetrabenzonitrile；tetrabenzonitrile copper(I) perchlorate；[Cu^I(PhCN)₄](ClO₄)；benzonitrile;copper(1+);perchlorate
• CAS: 15170-22-6
• 化学式: C₂₈H₂₀CuN₄*ClO₄
• 分子量: 575.49
• InChiKey: BOAHKOHEUYWBBL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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

• 作为反应物：
  描述：

  tetrakis(benzonitrile)copper(I) perchlorate 、 四甲基丙二胺 以 二氯甲烷 为溶剂， 生成 [(N¹, N¹, N³, N³-tetramethylpropane-1,3-diamine)Cu^I(PhCN)](ClO₄)
  参考文献：
  名称：

  Selective oxidation of exogenous substrates by a bis-Cu(III) bis-oxide complex: Mechanism and scope

  摘要：

  Cu(III)(2)(mu-O)(2) bis-oxides (O) form spontaneously by direct oxygenation of nitrogen-chelated Cu(I) species and constitute a diverse class of versatile 2e(-)/2H(+) oxidants, but while these species have attracted attention as biomimetic models for dinuclear Cu enzymes, reactivity is typically limited to intramolecular ligand oxidation, and systems exhibiting synthetically useful reactivity with exogenous substrates are limited. O-TMPD (TMPD = N-1, N-1, N-3, N-3-tetramethylpropane-1,3-diamine) presents an exception, readily oxidizing a diverse array of exogenous substrates, including primary alcohols and amines selectively over their secondary counterparts in good yields. Mechanistic and DFT analyses suggest substrate oxidation proceeds through initial axial coordination, followed by rate-limiting rotation to position the substrate in the Cu(III) equatorial plane, whereupon rapid deprotonation and oxidation by net hydride transfer occurs. Together, the results suggest the selectivity and broad substrate scope unique to O-TMPD are best attributed to the combination of ligand flexibility, limited steric demands, and ligand oxidative stability. In keeping with the absence of rate-limiting C-H scission, O-TMPD exhibits a marked insensitivity to the strength of the substrate C-alpha-H bond, readily oxidizing benzyl alcohol and 1-octanol at near identical rates.

  DOI：

  10.1016/j.ica.2018.11.027
• 作为产物：
  描述：

  铜 、 copper(II) perchlorate 以 苯甲腈 为溶剂， 生成 tetrakis(benzonitrile)copper(I) perchlorate
  参考文献：
  名称：

  Lewandowski, Andrzej; Malinska, Jadwiga, New Journal of Chemistry, 1996, vol. 20, # 6, p. 653 - 657

  摘要：

  DOI：

文献信息

• Solvation Behaviour of some Copper (I), Silver (I) and Tetraalkylammonium Salts in Actonitrile + Adiponitrile Mixtures
  作者：Dip Singh Gill、Dilbag Rana、Rahul Gupta

  DOI：10.1524/zpch.2008.5357

  日期：2008.7.1

  Solvation behaviour of some copper (I), silver (I) and tetrabutylammonium salts has been investigated in binary mixtures of acetonitrile and adiponitrile containing 100, 90, 80, 70, 60 and 50 mol % AN at 298 K using molar conductance and viscosity measurements. The conductance data have been analyzed by using the Shedlovsky method to calculate limiting molar conductance (Λ_o) of the electrolytes. The solvated radii for various ions indicate that tetrabutylammonium (Bu₄N⁺) and tetraphenylborate (BPh₄ ^–) are not solvated in all AN+ADN mixtures. The anions are poorly solvated but Cu⁺ and Ag⁺ are highly solvated in AN+ADN mixtures. The extent of solvation of Cu⁺ is greater then that of Ag⁺. The solvation of these both ions increases in ADN rich region of the mixtures. The viscosity data have been analyzed by using the Jones-Dole equation to calculate viscosity B-coefficients of electrolytes. The ionic B_± coefficients for individual ions have been evaluated. The results show that anions are weakly solvated in whole composition range of AN + ADN mixtures. The B₊ coefficients for Cu⁺ and Ag⁺ increase with increase in ADN composition i.e. these are better solvated in ADN rich region of binary mixtures. The viscosity results are in good agreement with the results obtained from the conductance studies.

  本研究使用摩尔电导率和粘度测量，研究了在含有100, 90, 80, 70, 60和50摩尔％的乙腈和己二腈的二元混合物中，一些铜（I）、银（I）和四丁基铵盐的溶解行为。使用Shedlovsky方法分析电导数据，计算电解质的极限摩尔电导率（Λo）。各种离子的溶剂化半径表明，四丁基铵（Bu4N+）和四苯基硼酸盐（BPh4-）在所有AN + ADN混合物中均未被溶剂化。阴离子溶剂化较差，但Cu+和Ag+在AN + ADN混合物中高度溶剂化。Cu+的溶剂化程度大于Ag+。这两种离子的溶剂化在混合物的ADN丰富区域增加。使用Jones-Dole方程分析粘度数据，计算电解质的粘度B系数。评估了各个离子的离子B±系数。结果表明，阴离子在AN + ADN混合物的整个组成范围内均溶解较弱。Cu+和Ag+的B+系数随着ADN组分的增加而增加，即在ADN丰富的二元混合物中更易溶解。粘度结果与电导研究结果相符。

• Nuclear Magnetic Resonance Studies of Copper(I) Complexes of Imidazoles. I. Their Preparation, Characterization, Equilibria, and Reaction with Carbon Monoxide
  作者：Susumu Kitagawa、Megumu Munakata

  DOI：10.1246/bcsj.59.2743

  日期：1986.9

  Various copper(I) complexes with monodentate imidazole(im) have been prepared from [Cu(CH3CN)4]X (X=ClO4− and PF6−) in acetone. Their characterization has principally been made by 1H NMR spectroscopy. Binary copper(I) complexes are [Cu(im)2]+ (2) and [Cu(im)3]+ (3), while the monoimidazole complex is a ternary two- or four-coordinate complex (1). In contrast with 2 and 3, quantitative formation of

  已经从丙酮中的 [Cu(CH3CN)4]X (X=ClO4- 和 PF6-) 制备了各种铜 (I) 与单齿咪唑 (im) 的配合物。它们的表征主要通过 1 H NMR 光谱法进行。二元铜(I)配合物是[Cu(im)2]+(2)和[Cu(im)3]+(3)，而单咪唑配合物是三元二或四配位配合物(1)。与 2 和 3 相比，[Cu(im)4]+ (4) 的定量形成不会在丙酮中发生。即使在 [im]/[Cu]<2 时，2 也比 1 更优先形成。这是由于 2 的线性结构。2 和 3 提供稳定的 CO 加合物，两者都显示完全可逆性。3 对 CO 的亲和力比 2 强得多。还制备了吡唑铜 (I) 配合物，并与咪唑配合物进行了比较。单齿吡唑几乎不产生二配位和三配位配合物。
• ⁶³Cu and¹⁰⁹Ag NMR studies of copper(<scp>I</scp>) and silver(<scp>I</scp>) salts in mixed solvents containing nitriles
  作者：Dip Singh Gill、Ludwig Rodehüser、Patrice Rubini、Jean-Jacques Delpuech

  DOI：10.1039/ft9959102307

  日期：——

  The solvation of copper(I) in mixed solvent systems containing acetonitrile or benzonitrile and the co-solvents propionitrile, butyronitrile, valeronitrile, as well as trimethyl-, triethyl- and tributyl-phosphite has been examined by 63Cu NMR and also, in the case of the phosphites, by 31P NMR. The concentration dependence and the variation of the chemical shift of the silver-109 signal with solvent composition have been studied in solutions of silver trifluoroacetate (AgO2CCF3).

  铜（I）在含有乙腈或苯腈以及共溶剂丙腈、丁腈、戊腈、亚磷酸三甲酯、亚磷酸三乙酯和亚磷酸三丁酯的混合溶剂体系中的溶解度已通过63Cu NMR进行了研究，对于亚磷酸酯，还通过31P NMR进行了研究。在三氟乙酸银（AgO2CCF3）溶液中，银-109信号的浓度依赖性和化学位移的变化已经过研究。
• Gill, Dip Singh; Pathania, Vivek; Vermani, Bal Krishan, Zeitschrift fur Physikalische Chemie, 2003, vol. 217, # 6, p. 739 - 749
  作者：Gill, Dip Singh、Pathania, Vivek、Vermani, Bal Krishan、Sharma, Raj Pal

  DOI：——

  日期：——
• Bowmaker, Graham A.; Gill, Dip Singh; Skelton, Brian W., Zeitschrift fur Naturforschung, B: Chemical Sciences, 2004, vol. 59, # 11-12, p. 1307 - 1313
  作者：Bowmaker, Graham A.、Gill, Dip Singh、Skelton, Brian W.、Somers, Neil、White, Allan H.

  DOI：——

  日期：——