(2,4,6-tri-tert-butylphenyl)[bis(dimethylamino)methylidene]phosphane | 562077-04-7

• 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: (2,4,6-tri-tert-butylphenyl)[bis(dimethylamino)methylidene]phosphane
• 英文别名: Mes(*)P=C(NMe2)2；N,N,N',N'-tetramethyl-1-(2,4,6-tritert-butylphenyl)phosphanylidenemethanediamine
• CAS: 562077-04-7
• 化学式: C₂₃H₄₁N₂P
• 分子量: 376.566
• InChiKey: MIBSRGUBIQLOQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2,4,6-tri-tert-butylphenyl)[bis(dimethylamino)methylidene]phosphane 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 以100%的产率得到[(2,4,6-tri-tert-butylphenyl)phosphino]bis(dimethylamino)carbenium chloride
  参考文献：
  名称：

  Phosphaalkenes with Inverse Electron Density:  Electrochemistry, Electron Paramagnetic Resonance Spectra, and Density Functional Theory Calculations of Aminophosphaalkene Derivatives

  摘要：

  Cyclic voltammetry of Mes*P=C(NMe2)(2) (1) and Mes*P=C(CH3)NMe2 (2) shows that, in solution in DME, these compounds are reversibly oxidized at 395 and 553 mV, respectively. Electrochemical oxidation or reaction of 1 (or 2) with [Cp2Fe]PF6 leads to the formation of the corresponding radical cation, which was characterized by its electron paramagnetic resonance (EPR) spectra. Experimental P-31 and C-13 isotropic and anisotropic coupling constants agree with density functional theory (DFT) calculations showing that the unpaired electron is strongly localized on the phosphorus atom, in accord with the description Mes*P-.-(C(NMe2)(2))(+). Electrochemical reduction of 1 is essentially irreversible and leads to a radical species largely delocalized on the C(NMe2)(2) moiety; this neutral radical results from the protonation of the phosphorus atom and corresponds to Mes*(H)P-C-.(NMe2)(2). No paramagnetic species is obtained by reduction of 2. The presence of the amino groups, responsible for the inverted electron distribution at the P-C double bond (P--C+), confers on 1 and 2 redox properties that are in very sharp contrast with those observed for phosphaalkenes with a normal pi electron distribution (P+-C-): no detection of the radical anion but easy formation of a rather persistent radical cation. For 1, this radical cation could even be isolated as a powder, 1(.+)PF(6)(-). As shown by DFT calculations, this behavior is consistent with the decrease of the double bond character of the phosphoruscarbon bond caused by the presence of the amino groups.

  DOI：

  10.1021/jp030023a
• 作为产物：
  描述：

  (2,4,6-三-叔-丁基苯基)膦 、 N,N,N,N-tetramethyldiamino ethoxycarbonium tetrafluoroborate 在 甲基锂 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以30%的产率得到(2,4,6-tri-tert-butylphenyl)[bis(dimethylamino)methylidene]phosphane
  参考文献：
  名称：

  Phosphaalkenes with Inverse Electron Density:  Electrochemistry, Electron Paramagnetic Resonance Spectra, and Density Functional Theory Calculations of Aminophosphaalkene Derivatives

  摘要：

  Cyclic voltammetry of Mes*P=C(NMe2)(2) (1) and Mes*P=C(CH3)NMe2 (2) shows that, in solution in DME, these compounds are reversibly oxidized at 395 and 553 mV, respectively. Electrochemical oxidation or reaction of 1 (or 2) with [Cp2Fe]PF6 leads to the formation of the corresponding radical cation, which was characterized by its electron paramagnetic resonance (EPR) spectra. Experimental P-31 and C-13 isotropic and anisotropic coupling constants agree with density functional theory (DFT) calculations showing that the unpaired electron is strongly localized on the phosphorus atom, in accord with the description Mes*P-.-(C(NMe2)(2))(+). Electrochemical reduction of 1 is essentially irreversible and leads to a radical species largely delocalized on the C(NMe2)(2) moiety; this neutral radical results from the protonation of the phosphorus atom and corresponds to Mes*(H)P-C-.(NMe2)(2). No paramagnetic species is obtained by reduction of 2. The presence of the amino groups, responsible for the inverted electron distribution at the P-C double bond (P--C+), confers on 1 and 2 redox properties that are in very sharp contrast with those observed for phosphaalkenes with a normal pi electron distribution (P+-C-): no detection of the radical anion but easy formation of a rather persistent radical cation. For 1, this radical cation could even be isolated as a powder, 1(.+)PF(6)(-). As shown by DFT calculations, this behavior is consistent with the decrease of the double bond character of the phosphoruscarbon bond caused by the presence of the amino groups.

  DOI：

  10.1021/jp030023a

文献信息

• Neue Kupferkomplexe mit Phosphaalkenliganden. Molekülstruktur von [Cu{P(Mes*)C(NMe2)2}2]BF4 (Mes* = 2,4,6-tBu3C6H2)
  作者：L. Weber、Jens Krümberg、H.-G. Stammler、B. Neumann

  DOI：10.1002/zaac.200600015

  日期：2006.4

  New Copper Complexes Containing Phosphaalkene Ligands. Molecular Structure of [CuP(Mes*)C(NMe2)2}2]BF4 (Mes* = 2,4,6-tBu3C6H2) Reaction of equimolar amounts of the inversely polarized phosphaalkene tBuP=C(NMe2)2 (1a) and copper(I) bromide or copper(I) iodide, respectively, affords complexes [Cu3X3μ-P(tBu)C(NMe2)2}3] (2) (X =Br) and (3) (X = I) as the formal result of the cyclotrimerization of a 1:1-adduct

  含有磷烯烃配体的新型铜配合物。[CuP(Mes*)C(NMe2)2}2]BF4 的分子结构 (Mes* = 2,4,6-tBu3C6H2) 等摩尔量的反极化磷烯烃 tBuP=C(NMe2)2 (1a) 的反应) 和溴化铜 (I) 或碘化铜 (I) 分别提供复合物 [Cu3X3μ-P(tBu)C(NMe2)2}3] (2) (X =Br) 和 (3) (X = I) 作为 1:1 加合物环三聚的正式结果。用 [Cu(L)Cl] (L = PiPr3; SbiPr3) 处理 1a 导致形成化合物 [CuCl(L)P(tBu)C(NMe2)2}] (4a) (L = PiPr3) 和(4b) (L = SbiPr3)，分别。[(MeCN)4Cu]BF4 与两当量的 PhP=C(NMe2)2 (1b) 反应生成复合物 [CuP(Ph)C(NMe2)2}2]BF4 (5b)。类似地，化合物
• Two phosphaalkene radical cations with inverse spin density distributions
  作者：Xiaobo Pan、Xingyong Wang、Zaichao Zhang、Xinping Wang

  DOI：10.1039/c5dt00656b

  日期：——

  Two phosphaalkene radical cations 1˙+ and 2˙+ have been reported. 1˙+ is stable in the solid state and has been structurally characterized. 2˙+ only remains persistent in solution. 1˙+ is described as a phosphorus-centered radical, while 2˙+ as a delocalized radical with little contribution from phosphorus.

  已经报道了两个磷烯烃自由基阳离子1 +和2 +。1˙ +在固态下是稳定的，并且已经在结构上进行了表征。2˙ +仅在解决方案中保持不变。1 + +被描述为一个以磷为中心的自由基，而2 + +被描述为一个离域的自由基，几乎没有磷的贡献。
• Phosphaalkenes with Inverse Electron Density:  Electrochemistry, Electron Paramagnetic Resonance Spectra, and Density Functional Theory Calculations of Aminophosphaalkene Derivatives
  作者：Patrick Rosa、Cyril Gouverd、Gérald Bernardinelli、Théo Berclaz、Michel Geoffroy

  DOI：10.1021/jp030023a

  日期：2003.6.1

  Cyclic voltammetry of Mes*P=C(NMe2)(2) (1) and Mes*P=C(CH3)NMe2 (2) shows that, in solution in DME, these compounds are reversibly oxidized at 395 and 553 mV, respectively. Electrochemical oxidation or reaction of 1 (or 2) with [Cp2Fe]PF6 leads to the formation of the corresponding radical cation, which was characterized by its electron paramagnetic resonance (EPR) spectra. Experimental P-31 and C-13 isotropic and anisotropic coupling constants agree with density functional theory (DFT) calculations showing that the unpaired electron is strongly localized on the phosphorus atom, in accord with the description Mes*P-.-(C(NMe2)(2))(+). Electrochemical reduction of 1 is essentially irreversible and leads to a radical species largely delocalized on the C(NMe2)(2) moiety; this neutral radical results from the protonation of the phosphorus atom and corresponds to Mes*(H)P-C-.(NMe2)(2). No paramagnetic species is obtained by reduction of 2. The presence of the amino groups, responsible for the inverted electron distribution at the P-C double bond (P--C+), confers on 1 and 2 redox properties that are in very sharp contrast with those observed for phosphaalkenes with a normal pi electron distribution (P+-C-): no detection of the radical anion but easy formation of a rather persistent radical cation. For 1, this radical cation could even be isolated as a powder, 1(.+)PF(6)(-). As shown by DFT calculations, this behavior is consistent with the decrease of the double bond character of the phosphoruscarbon bond caused by the presence of the amino groups.