2,2,6,6-tetramethyl-3,5-heptadionato ion | 122031-37-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2,6,6-tetramethyl-3,5-heptadionato ion
• 英文别名: 2,2,6,6-Tetramethyl-5-oxohept-3-en-3-olate
• CAS: 122031-37-2
• 化学式: C₁₁H₁₉O₂
• 分子量: 183.271
• InChiKey: SOZFXLUMSLXZFW-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2,6,6-tetramethyl-3,5-heptadionato ion 在 copper(l) iodide 、 cesiumhydroxide monohydrate 、 cesium(I) carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 [copper(I)(2,2,6,6-tetramethyl-3,5-heptanedione(-H))(OPh)](1-)
  参考文献：
  名称：

  Discriminating role of bases in diketonate copper(i)-catalyzed C–O couplings: phenol versus diarylether

  摘要：

  研究了由碘苯（PhI）和氢氧化铯（CsOH）在铜(I)催化下生成苯酚的机制，该铜(I)与由2,2,6,6-四甲基-3,5-庚二酮（TMHD）生成的1,3-二酮配体（ket²）结合。通过与实验技术（循环伏安法、1H NMR和ESI-MS）结合的DFT计算进行了研究。[(ket²)CuI–OH]⁻中负电荷的氧原子与PhI之间的微弱卤素键合引发氧化加成，生成(ket²)CuIII(Ph)–OH。后者经历较快的还原消除反应，从中释放出(ket²)CuI(PhOH)和苯酚（PhOH）。在额外的碱性氢氧化铯（Cs2CO3）存在下，形成二苯醚（PhOPh）。PhOH或PhOPh的两个催化循环在(ket²)CuI(PhOH)层面上分支，后者在CsOH存在下可以生成PhOH，或者被Cs2CO3去质子化，生成[(ket²)CuI–OPh]⁻。[(ket²)CuI–OPh]⁻与PhI的氧化加成导致(ket²)CuIII(Ph)–OPh，参与更快的还原消除，最终生成二苯醚（PhOPh）和CuI催化剂。

  DOI：

  10.1039/c3dt32948h
• 作为产物：
  描述：

  2,2,6,6-四甲基-3,5-庚二酮 在 cesiumhydroxide monohydrate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 2,2,6,6-tetramethyl-3,5-heptadionato ion
  参考文献：
  名称：

  Discriminating role of bases in diketonate copper(i)-catalyzed C–O couplings: phenol versus diarylether

  摘要：

  研究了由碘苯（PhI）和氢氧化铯（CsOH）在铜(I)催化下生成苯酚的机制，该铜(I)与由2,2,6,6-四甲基-3,5-庚二酮（TMHD）生成的1,3-二酮配体（ket²）结合。通过与实验技术（循环伏安法、1H NMR和ESI-MS）结合的DFT计算进行了研究。[(ket²)CuI–OH]⁻中负电荷的氧原子与PhI之间的微弱卤素键合引发氧化加成，生成(ket²)CuIII(Ph)–OH。后者经历较快的还原消除反应，从中释放出(ket²)CuI(PhOH)和苯酚（PhOH）。在额外的碱性氢氧化铯（Cs2CO3）存在下，形成二苯醚（PhOPh）。PhOH或PhOPh的两个催化循环在(ket²)CuI(PhOH)层面上分支，后者在CsOH存在下可以生成PhOH，或者被Cs2CO3去质子化，生成[(ket²)CuI–OPh]⁻。[(ket²)CuI–OPh]⁻与PhI的氧化加成导致(ket²)CuIII(Ph)–OPh，参与更快的还原消除，最终生成二苯醚（PhOPh）和CuI催化剂。

  DOI：

  10.1039/c3dt32948h

文献信息

• Studies on Mixed Chelates. XIV. Influences of Solvent Polarity, and of Substituent Groups in β-Diketonate Ligands, on the Electronic Spectra of 5-Coordinated Mixed Copper(II) Chelates in Organic Solutions
  作者：Yutaka Fukuda、Mayumi Yasuhira、Kozo Sone

  DOI：10.1246/bcsj.58.3518

  日期：1985.12

  Several chelates of copper(II), Cu(tmen)(dike)X, were newly obtained where tmen=N,N,N′,N′-tetramethylethylenediamine, dike= a β-diketonate ion, and X−= a halide or pseudohalide anion. These complexes exist as 5-coordinated species, with axially coordinated X−, in nonpolar solvents. In more polar solvents, they are ionized according to the solvent polarity, and form the following equilibrium mixtur

  新获得了铜 (II)、Cu(tmen)(dike)X 的几种螯合物，其中 tmen=N,N,N',N'-四甲基乙二胺，dike= β-二酮离子，并且 X-= 卤化物或假卤化物阴离子。在非极性溶剂中，这些配合物以 5 配位物种存在，具有轴向配位的 X-。在极性更大的溶剂中，它们根据溶剂极性被电离，并形成以下平衡混合物：[Cu(tmen)(dike)X]\ightleftharpoons[Cu(tmen)(dike)]++X−5–coordinated 4 – 配位（溶剂化，四方）该平衡由（a）溶剂的受体和供体性质的强度控制，可以通过其极性因子（Pf）表示，即供体数量和受体数量的线性组合的溶剂，
• Design of carbazole-based platinum complexes with steric hindrance for efficient organic light-emitting diodes
  作者：Xu-Feng Luo、Sheng Ning、Hang He、Hao Tang、Liang-Jun Shen、Yi-Rui Shen、Hua-Bo Han、Xunwen Xiao、You-Xuan Zheng

  DOI：10.1039/d3dt02264a

  日期：——

  The construction of platinum complexes with high steric hindrance is expected to suppress triple–triplet annihilation and π–π stacking to achieve high-performance organic light-emitting diodes (OLEDs) with low efficiency roll-off. Herein, two large steric hindrance platinum complexes (N-CzPhPtacac and N-CzCF3PhPtacac) were prepared by taking advantage of steric hindrance between the phenyl group on

  具有高空间位阻的铂配合物的结构有望抑制三重态湮灭和π-π堆积，从而实现低效率滚降的高性能有机发光二极管（OLED）。本文利用咔唑上的苯基与3位官能团（苯基和三氟甲基取代的苯基）之间的空间位阻，制备了两种大位阻铂配合物（N -CzPhPtacac和N -CzCF 3 PhPtacac）。吡啶部分。由于HOMO和LUMO之间相似的电子云分布和能隙差异，两种配合物在590和596 nm处表现出相似的橙红色发射峰，PL量子产率高达90%和92%，激发态寿命较短，分别为2.77和596 nm。掺杂薄膜中分别为 3.08 μs。因此，基于N -CzPhPtacac和N -CzCF 3 PhPtacac的OLED分别表现出15.4%和18.9%的最大外量子效率（EQE max ）值。重要的是，受益于-CF 3效应带来的更拉伸的空间配置，相应的OLED表现出较低的效率滚降，在1000 cd m -2时EQE为18
• Temperature-Dependent Rate Constants for the Reactions of Gas-Phase Lanthanides with O₂
  作者：Mark L. Campbell

  DOI：10.1021/jp991647c

  日期：1999.9.1

  The reactivity of the gas-phase lanthanide atoms Ln (Ln = La-Yb with the exception of Pm) with O-2 is reported. Lanthanide atoms were produced by the photodissociation of [Ln(TMHD)(3)] and detected by laser-induced fluorescence. For all the lanthanides studied with the exception of Yb, the reaction mechanism is bimolecular abstraction of an oxygen atom. The bimolecular rate constants (in molecule(-1) cm(3) s(-1)) are described in Arrhenius form by k[Ce((1)G(4))] = (3.0 +/- 0.4) x 10(-10) exp(-3.4 +/- 1.3 kJ mol(-1)/RT); Pr(I-4(9/2)), (3.1 +/- 0.7) x 10(-10) exp(-5.3 +/- 1.5 kJ mol(-1)/RT); Nd(I-5(4)), (3.6 +/- 0.3) x 10(-10) exp(-6.2 +/- 0.4 kJ mol(-1)/RT); Sm(F-7(0)), (2.4 +/- 0.4) x 10(-10) exp(-6.2 +/- 1.5 kJ mol(-1)/RT); EU(S-8(7/2)), (1.7 +/- 0.3) x 10(-10) exp(-9.6 +/- 0.7 kJ mol(-1)/RT); Gd(D-9(2)), (2.7 +/- 0.3) x 10(-10) exp(-5.2 +/- 0.8 kJ mol(-1)/RT); Tb(H-6(15/2)), (3.5 +/-. 0.6) x 10(-10) exp(-7.2 +/- 0.8 kJ mol(-1)/RT); Dy(I-5(8)), (2.8 +/- 0.6) x 10(-10) exp(-9.1 +/- 0.9 kJ mol(-1)/RT); Ho(I-4(15/2),), (2.4 +/- 0.4) x 10(-10) exp(-9.4 +/- 0.8 kJ mol(-1)/RT); Er(H-3(6)), (3.0 +/- 0.8) x 10(-10) exp(-10.6 +/- 1.1 kJ mol(-1)/RT); Tm(F-2(7/2)), (2.9 +/- 0.2) x 10(-10) exp(-11.1 +/- 0.4 kJ mol(-1)/RT), where the uncertainties represent +/-2 sigma. The reaction barriers are found to correlate to the energy required to promote an electron out of the 6s subshell. The reaction of Yb(S-1(0)) with O-2 reacts through a termolecular mechanism. The limiting low-pressure third-order rate constants are described in Arrhenius form by k(0)[Yb(S-1(0))] = (2.0 +/- 1.3) x 10(-28) exp(-9.5 +/- 2.8 kJ mol(-1)/RT) molecule(-2) cm(6) s(-1).
• Discriminating role of bases in diketonate copper(i)-catalyzed C–O couplings: phenol versus diarylether
  作者：Guillaume Lefèvre、Anis Tlili、Marc Taillefer、Carlo Adamo、Ilaria Ciofini、Anny Jutand

  DOI：10.1039/c3dt32948h

  日期：——

  The mechanism of the formation of phenol from PhI and CsOH catalysed by copper(I) ligated to the 1,3-diketonate ket′− generated from 2,2,6,6-tetramethyl-3,5-heptanedione (TMHD) has been investigated by DFT calculations associated with experimental techniques: cyclic voltammetry, 1H NMR, and ESI-MS. Weak halogen bonding between the negatively charged O atom of [(ket′)CuI–OH]− and PhI leads to an oxidative addition that gives (ket′)CuIII(Ph)–OH. The latter undergoes a faster reductive elimination that delivers (ket′)CuI(PhOH) from which PhOH is released. PhOPh is formed in the presence of an extra base Cs2CO3. The two catalytic cycles of formation of PhOH or PhOPh are branched at the level of (ket′)CuI(PhOH) that can either afford PhOH in the presence of CsOH or be deprotonated by Cs2CO3 to generate [(ket′)CuI–OPh]−. The oxidative addition of [(ket′)CuI–OPh]− to PhI leads to (ket′)CuIII(Ph)–OPh involved in a faster reductive elimination that delivers PhOPh and the CuI catalyst.

  研究了由碘苯（PhI）和氢氧化铯（CsOH）在铜(I)催化下生成苯酚的机制，该铜(I)与由2,2,6,6-四甲基-3,5-庚二酮（TMHD）生成的1,3-二酮配体（ket²）结合。通过与实验技术（循环伏安法、1H NMR和ESI-MS）结合的DFT计算进行了研究。[(ket²)CuI–OH]⁻中负电荷的氧原子与PhI之间的微弱卤素键合引发氧化加成，生成(ket²)CuIII(Ph)–OH。后者经历较快的还原消除反应，从中释放出(ket²)CuI(PhOH)和苯酚（PhOH）。在额外的碱性氢氧化铯（Cs2CO3）存在下，形成二苯醚（PhOPh）。PhOH或PhOPh的两个催化循环在(ket²)CuI(PhOH)层面上分支，后者在CsOH存在下可以生成PhOH，或者被Cs2CO3去质子化，生成[(ket²)CuI–OPh]⁻。[(ket²)CuI–OPh]⁻与PhI的氧化加成导致(ket²)CuIII(Ph)–OPh，参与更快的还原消除，最终生成二苯醚（PhOPh）和CuI催化剂。