N,N'-bis(mesityl)bis(diphenylphosphinoimino)methane | 288263-06-9

• 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: N,N'-bis(mesityl)bis(diphenylphosphinoimino)methane
• 英文别名: H2C(PPh2NMes)2；CH2(Ph2P=N-2,4,6-Me3C6H2)2；CH2(Ph2PNC6H2-Me3-2,4,6)2；[Diphenyl-(2,4,6-trimethylphenyl)imino-lambda5-phosphanyl]methyl-diphenyl-(2,4,6-trimethylphenyl)imino-lambda5-phosphane；[diphenyl-(2,4,6-trimethylphenyl)imino-λ5-phosphanyl]methyl-diphenyl-(2,4,6-trimethylphenyl)imino-λ5-phosphane
• CAS: 288263-06-9
• 化学式: C₄₃H₄₄N₂P₂
• 分子量: 650.783
• InChiKey: RHYYHWPWFICBRN-UHFFFAOYSA-N

物化性质

• 沸点：
  786.4±70.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.9
• 重原子数：
  47
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N,N'-bis(mesityl)bis(diphenylphosphinoimino)methane 在 正丁基锂 作用下， 生成 Li[HC(Ph2PNdipp)2]
  参考文献：
  名称：

  第1组双（亚氨基正膦酸酯）甲烷，第2部分：立体要求甲烷H 2 C（PPh 2 NR）2（R = 2,4,6-三甲基苯基或2,6-二异丙基苯基）的N-芳基衍生物

  摘要：

  用1当量的[Na（Bn）]（Bn = CH 2 C 6 H 5）在THF中处理H 2 C（PPh 2 NMes）2（Mes = 2,4,6-三甲基苯基），得到路易斯碱加合物[ Na {HC（PPh 2 NMes）2 }（THF）2 ]（1）。通过[MOR]的反应，制备了重金属1甲烷化物[Rb {HC（PPh 2 NMes）2 }（DME）2 ]（2）和[Cs {HC（PPh 2 NMes）2 }] 6（3）。 （M = Cs，Rb; OR = 2-乙基己氧化物）与[Li {HC（PPh 2 NMes）2 }]。路易斯碱加合物2是单体的，但是即使从强供体溶剂THF中重结晶，路易斯3也以新型环状2.9nm六聚体的形式存在。H 2 C（PPh 2 NDipp）2（Dipp ＝ 2，6-二异丙基苯基）与[Na（Bn）]的反应得到[Na {HC（PPh 2 NDipp）2 }（THF）]（4）。通过母体甲烷与KH反应制得钾同类物[K

  DOI：

  10.1021/om200729x
• 作为产物：
  描述：

  2,4,6-三甲基苯胺 在 盐酸 、 sodium azide 作用下， 以 甲苯 为溶剂， 反应 4.33h， 生成 N,N'-bis(mesityl)bis(diphenylphosphinoimino)methane
  参考文献：
  名称：

  Al-Benna, Sarah; Sarsfield, Mark J.; Thornton-Pett, Mark, Journal of the Chemical Society, Dalton Transactions, 2000, # 23, p. 4247 - 4257

  摘要：

  DOI：

文献信息

• Bis(phosphinimino)methyl derivatives of Ca, Sr and Ba: facile access to heavier alkaline earth organometallic chemistry
  作者：Michael S. Hill、Peter B. Hitchcock

  DOI：10.1039/b305430f

  日期：——

  A series of mononuclear and arene-soluble bis(phosphinimino)methyl derivatives of the heavier alkaline earth metals, calcium, strontium and barium, have been obtained by straightforward addition of two molar equivalents of [KN(SiMe3)2] to a mixture of [CH2(Ph2PNC6H2-Me3-2,4,6)2] and MI2 (M = Ca, Sr, Ba) in THF.

  通过将两个摩尔当量的 [KN(SiMe3)2] 直接添加到 [...] THF 中的 CH2(Ph2PNC6H2-Me3-2,4,6)2] 和 MI2 (M = Ca, Sr, Ba)。
• Synthesis of C2 and Cs symmetric zinc complexes supported by bis(phosphinimino)methyl ligands and their use in ring opening polymerisation catalysis
  作者：Michael S. Hill、Peter B. Hitchcock

  DOI：10.1039/b207358g

  日期：2002.12.9

  Synthetic routes to zinc complexes supported by sterically demanding bis(phosphinimino)methyl ligands are reported. Two aryl-substituted ligand precursors have been utilised, [CH2(Ph2PNC6H2Me3-2,4,6)2], 1, and [CH2(Ph2PNPh)(Ph2PNC6H2Me3-2,4,6)], 2. The second of these is the first example of an asymmetric bis(phosphinimino)methane. These ligands are converted to three-coordinate RZnX complexes (R = 1; X = Me, N(SiMe3)2; R = 2; X = Me) with either C2 or Cs symmetry in solution by reaction with either ZnMe2 or Zn[N(SiMe3)2]2 in toluene. All three derivatives have been shown to exist as three-coordinate monomers in the solid state by X-ray diffraction analysis. Protonolysis of these compounds with the bulky phenol 2,4-tBu2C6H3OH or triphenylmethanol resulted in the isolation of a series of three-coordinate aryloxy or alkoxyzinc derivatives. In contrast, reaction with less sterically demanding alcohols resulted in protonation of the bis(phosphinimino)methyl ligand. A similar result was obtained from reaction of RZnMe (R = 1) and triphenylsilanol and the product is the first example of a bis(triorganosiloxy)zinc compound to be structurally characterised. All the compounds have been examined for activity in ring opening polymerisation catalysis of rac-lactide. The aryloxy and triphenylmethoxy derivatives are active catalysts; however, no evidence of true ‘living’ behaviour or stereocontrol of diastereomer insertion has been observed.

  本研究报告介绍了由立体要求较高的双(膦酰亚胺)甲基配体支持的锌配合物的合成路线。我们使用了两种芳基取代配体前体：[CH2(Ph2PNC6H2Me3-2,4,6)2]，1 和 [CH2(Ph2PNPh)(Ph2PNC6H2Me3-2,4,6)]，2。 其中第二种是不对称双（膦酰亚胺）甲烷的第一个实例。通过与 ZnMe2 或 Zn[N(SiMe3)2]2 在甲苯中反应，这些配体在溶液中被转化为具有 C2 或 Cs 对称性的三配位 RZnX 复合物（R = 1; X = Me, N(SiMe3)2; R = 2; X = Me）。X 射线衍射分析表明，所有这三种衍生物在固态下都是三配位单体。用笨重的苯酚 2,4-tBu2C6H3OH 或三苯基甲醇对这些化合物进行质子分解，可分离出一系列三配位芳氧基或烷氧锌衍生物。相反，与立体要求较低的醇反应则会导致双（膦酰亚胺）甲基配体质子化。RZnMe （R = 1）与三苯基硅醇的反应也得到了类似的结果，该产物是第一个在结构上得到表征的双（三有机硅氧基）锌化合物实例。我们对所有化合物在催化 rac-lactide 开环聚合过程中的活性进行了研究。芳氧基和三苯甲氧基衍生物是活性催化剂，但没有观察到真正的 "活 "行为或非对映异构体插入的立体控制。
• Group 1 and 13 complexes of aryl-substituted bis(phosphinimino)methyls
  作者：Michael S Hill、Peter B Hitchcock、Sophia M.A Karagouni

  DOI：10.1016/j.jorganchem.2003.11.030

  日期：2004.2

  The organolithium reagent [HC(Ph2PNC6H2Me3-2,4,6)2}Li(OEt2)] was easily obtained by deprotonation of H2C(Ph2PNC6H2Me3-2,4,6)2 with nBuLi in diethyl ether solution. The crystal structure of [HC(Ph2PNC6H2Me3-2,4,6)2}Li(OEt2)] has been determined and shown to consist a monomeric chelate structure that contains a distorted, trigonal planar lithium centre. The ligand precursor has also been deprotonated

  有机锂试剂[HC（PH 2 PNC 6 ħ 2我3 -2,4,6-）2 }李（OET 2）]很容易被去质子化得到ħ 2 C（博士2 PNC 6 ħ 2我3 -n，2,4,6）2与nBuLi的乙醚溶液。[HC（Ph 2 PNC 6 H 2 Me 3 -2,4,6）2 } Li（OEt 2）]已确定并显示为包含螯合物的单体螯合物结构，该结构具有扭曲的三角平面锂中心。配体前体也已用Me 3 Al和Me 2 AlCl进行了质子化反应，得到了四面体有机铝络合物[HC（Ph 2 PNC 6 H 2 Me 3 -2,4,6）2 } AlMe 2 ]和[ HC（Ph 2 PNC 6 H 2 Me 3 -2,4,6）2 } Al（Cl）Me]。[HC（Ph 2 PNC 6 H 2 Me 3 -2,4,6）2 } Li（OEt2）]与AlX 3（X = Cl，Br，I）或GaCl 3生成一系列二卤代衍生物[HC（Ph
• Synthesis and structure of [U{C(PPh2NMes)2}2] (Mes = 2,4,6-Me3C6H2): A homoleptic uranium bis(carbene) complex with two formal UC double bonds
  作者：Oliver J. Cooper、Jonathan McMaster、William Lewis、Alexander J. Blake、Stephen T. Liddle

  DOI：10.1039/c0dt00152j

  日期：——

  Treatment of H2C(PPh2NMes)2 (1, Mes = 2,4,6-Me3C6H2) with two equivalents of ButLi afforded the methandiide complex [Li2C(PPh2NMes)2}2]2 (2); reaction of 2 with [UI3(THF)4] gave [UC(PPh2NMes)2}2] (3), which is the first homoleptic uranium bis(carbene) complex with two formal UC double bonds.

  H的治疗2 C（PPH 2个的NME）2（1，MES = 2,4,6-ME 3 c ^ 6 ħ 2）与卜两个当量吨栗，得到二甲双胍 复杂的 [Li 2 C（PPh 2 NMES）2 } 2 ] 2（2）; 的反应2与[UI 3（THF）4〕得到〔U C（PPh 2 NMES）2 } 2]（3），这是第一个均质剂铀双（卡宾）具有两个正式的U C双键的复合物。
• Synthesis of a homoleptic Sm(ii) bis(phosphinimino)methanide
  作者：Michael S. Hill、Peter B. Hitchcock

  DOI：10.1039/b313034g

  日期：——

  Reaction of two molar equivalents of [KN(SiMe3)2] and a mixture of [CH2(Ph2PNC6H2-Me3-2,4,6)2] and SmI2 in THF resulted in the formation of a stable homoleptic samarium dialkyl without additional solvent coordination.

  将两个摩尔当量的[KN(SiMe3)2]与[CH2(Ph2PNC6H2-Me3-2,4,6)2]和 SmI2 的混合物在四氢呋喃中反应，形成了稳定的同色二烷基钐，而无需额外的溶剂配位。