(2,4-di-tert-butyl-6-((2-[(3,5-di-tert-butyl-2-hydroxy-benzylidene)-amino]-phenylimino)-methyl)-phenolato)copper(II) | 777943-61-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (2,4-di-tert-butyl-6-((2-[(3,5-di-tert-butyl-2-hydroxy-benzylidene)-amino]-phenylimino)-methyl)-phenolato)copper(II)
• 英文别名: [Cu(N,N'-phenylenebis(3,5-di-tert-butylsalicylideneimine)-1H)]；[Cu(3,5-tBu2-salophen)]
• CAS: 777943-61-0
• 化学式: C₃₆H₄₆CuN₂O₂
• 分子量: 602.319
• InChiKey: LCPBWVXLCNOPQW-XWOQVIMMSA-L

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：

  (2,4-di-tert-butyl-6-((2-[(3,5-di-tert-butyl-2-hydroxy-benzylidene)-amino]-phenylimino)-methyl)-phenolato)copper(II) 以 二氯甲烷 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Electron and energy-transfer reactions of with copper-phenolates

  摘要：

  Covalently-modified tyrosines are found as cofactors in enzymes such as galactose oxidase and the copper-dependent amine oxidases. In these cases, cofactor formation has been proposed to occur via oxidation of a copper-tyrosine precursor, making electron transfer chemistry in copper-phenolates a key to cofactor biogenesis. Our work was motivated by a desire to understand the ET reactivity of simple metal coordinated phenolate model complexes. Copper and zinc complexes of phenolate ligands were prepared, and their electron and energy-transfer reactivity toward Ru(R(2)bpy)(3)(2+)*(/3+) studied to test the electron-transfer reactivity of metal-coordinated phenolates. M(salxn) (M = Cu2+ Zn2+; salxn = salen, N,N'-disalicylidene-1,2-ethylenediamine; salpen, N,N'-disalicylidene-1,3-propylenediamine; salben, N,N'-disalicylidene-1,4-butylenediamine: salophen, N,N'-disalicylidene-o-phenylenediamine) were synthesized along with the more easily oxidized complexes Cu(bppa) (Hbppa, bis-pyridyl phenolamine) and Cu(icoph) (H(2)icoph, bis-iminocatechol o-phenylenediamine). Zn(salophen) and Cu(salophen) were oxidized by Ru(bpy)(3)(3+), indicating that electron transfer was thermodynamically favorable. Cu(salxn) complexes were observed to be efficient energy-transfer quenchers of Ru(bpy)(3)(2+)*; in contrast, Cu(bppa) and Cu(icoph) quenched Ru(bpy)3(2+)* by electron transfer, with observed reorganization energy lambda = 22 kcal/mol. The large self-exchange reorganization energy calculated for the Cu-coordinated phenolates suggest that the CAO and GalOx cofactors may be poor 1e(-) redox centers, with very slow rates for cofactor biogenesis. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2008.07.016
• 作为产物：
  描述：

  N,N'-bis-(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamine 、 copper(II) nitrate trihydrate 在 NaOH 作用下， 以 乙醇 为溶剂， 以82%的产率得到(2,4-di-tert-butyl-6-((2-[(3,5-di-tert-butyl-2-hydroxy-benzylidene)-amino]-phenylimino)-methyl)-phenolato)copper(II)
  参考文献：
  名称：

  M（3,5- t Bu 2 -salophen）（M = Cu，VO）的合成及X射线结构表征

  摘要：

  报道了Cu（3,5- t Bu 2 -salophen）（4）和VO（3,5- t Bu 2 -salophen）（5）的合成，表征以及晶体结构的阐明。X射线分析分别显示了结构4和结构5中预期的近似方形铜（II）平面几何形状和钒的方形金字塔形几何形状。两种离散的分子结构均定义良好，不存在明显的氢键。4和5的EPR谱图是此类复合物的典型特征。3,5- t Bu 2 -salophen =  N，Ñ '-phenylenebis（3,5-二-叔-butylsalicylideneimine）。

  DOI：

  10.1016/j.poly.2005.07.018

文献信息

• Characterization of one-electron oxidized copper(<scp>ii</scp>)-salophen-type complexes; effects of electronic and geometrical structures on reactivities
  作者：Kazutaka Asami、Akiko Takashina、Misato Kobayashi、Satoshi Iwatsuki、Tatsuo Yajima、Amélie Kochem、Maurice van Gastel、Fumito Tani、Takamitsu Kohzuma、Fabrice Thomas、Yuichi Shimazaki

  DOI：10.1039/c3dt52338a

  日期：——

  investigated. The solid state structures of the one-electron oxidized forms of these complexes suggested that [Cu(salophen)]+ and [Cu(MeO-salophen)]+ can be assigned to relatively localized Cu(II)-phenoxyl radical complexes, while [Cu(salophen-(MeO)2)]+ is the diiminobenzene radical complex. On the other hand, [Cu(salophen)]+ in solution showed a different electronic structure from that of the solid sample

  单电子氧化的Salophen型配合物[Cu（salophen）] +（H 2 salophen = N，N'-双（3,5-二叔丁基水杨基）-1,2-二氨基苯）及其甲氧基衍生物，[Cu（MEO-salophen）] +和[Cu（salophen-（MEO）2）] +（H 2 MEO-salophen = N，N'-双（3-叔丁基-5-甲氧基水杨基）-1，二氨基苯，H 2 salophen-（MEO）2 = ñ，ñ ' -双（3,5-二-叔合成了（丁基丁基水杨基）-1，2-二氨基-4，5-二甲氧基苯），并对其结构进行了表征，并对它们的反应性进行了研究。这些络合物的单电子氧化形式的固态结构表明[Cu（salophen）] +和[Cu（MEO-salophen）] +可以分配给相对局部的Cu（II）-苯氧基自由基络合物，而[ Cu（salophen-（MEO）2）] +是二亚氨基苯自由基配合物。另一方面，[Cu（salophen）]
• Intramolecularly hydrogen-bonded versus copper(<scp>ii</scp>) coordinated mono- and bis-phenoxyl radicals
  作者：Fabrice Thomas、Olivier Jarjayes、Carole Duboc、Christian Philouze、Eric Saint-Aman、Jean-Louis Pierre

  DOI：10.1039/b406009a

  日期：——

  electrochemically oxidized. The mono-phenoxyl radical species are X-band EPR silent. The bis-phenoxyl radical species exhibits a (S= 3/2) ground state: it arises from a ferromagnetic exchange coupling between the two spins of the radicals and that of the copper(II) when the spacer is rigid enough; a flexible spacer such as ethylidene induces decomplexation of at least one phenoxyl group. Metal coordination is more

  带有两个在邻位和对位被叔丁基取代的水杨叉二亚胺亚胺基团的配体已经被电化学氧化为单和双苯氧基基团。该方法涉及与电子转移偶联的分子内质子，并提供其中氧原子氢键合到质子化铵或亚胺基团上的基团。双自由基物质中的两个苯氧基部分之间存在弱的分子内偶极相互作用。这些配体的铜（II）配合物已被表征并被电化学氧化。单苯氧基基团是X带EPR沉默的。双苯氧基自由基物种具有（S = 3/2）基态：当间隔基足够刚性时，它是由自由基的两个自旋与铜（II）的自旋之间的铁磁交换耦合引起的。诸如亚乙基的柔性间隔基引起至少一个苯氧基的分解。金属配位比氢键更有效，以增强单苯氧基自由基的化学稳定性。