bis(N-p-tolyliminodiphenylphosphoranyl)methane | 33535-76-1

• 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: bis(N-p-tolyliminodiphenylphosphoranyl)methane
• 英文别名: bis(p-tolyl-imino-diphenylphosphoranyl)methane；bis(p-tolyliminodiphenylphosphoranyl)methane；(4-Methylphenyl)imino-[[(4-methylphenyl)imino-diphenyl-lambda5-phosphanyl]methyl]-diphenyl-lambda5-phosphane；(4-methylphenyl)imino-[[(4-methylphenyl)imino-diphenyl-λ5-phosphanyl]methyl]-diphenyl-λ5-phosphane
• CAS: 33535-76-1
• 化学式: C₃₉H₃₆N₂P₂
• 分子量: 594.676
• InChiKey: JITPQGHHBBHPOJ-UHFFFAOYSA-N

物化性质

• 沸点：
  734.7±70.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.4
• 重原子数：
  43
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  bis(N-p-tolyliminodiphenylphosphoranyl)methane 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以100%的产率得到sodium-bis(p-tolyl-imino-diphenylphosphoranyl)methanide
  参考文献：
  名称：

  Imhoff, P.; van Asselt, R.; Elsevier, C. J., Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 47, p. 401 - 415

  摘要：

  DOI：
• 作为产物：
  描述：

  p-叠氮甲苯 、 双二苯基膦甲烷 以 苯 为溶剂， 反应 4.0h， 以98%的产率得到bis(N-p-tolyliminodiphenylphosphoranyl)methane
  参考文献：
  名称：

  Imhoff, P.; van Asselt, R.; Elsevier, C. J., Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 47, p. 401 - 415

  摘要：

  DOI：

文献信息

• Synthesis and stability of Li/Cl carbenoids based on bis(iminophosphoryl)methanes
  作者：Kai-Stephan Feichtner、Viktoria H. Gessner

  DOI：10.1039/c4dt01466a

  日期：——

  bis(iminophosphoryl) substituted lithium chloride carbenoids with different N-substituents (tolyl and adamantyl) were examined. Their preparation was accomplished via the mild oxidation of the corresponding dilithio bis(iminophosphoryl) methandiides, BIPMTol and BIPMAd, which are easily accessible by direct double deprotonation. In the case of the adamantyl substituted system the alternative preparation method via

  研究了两种具有不同N-取代基（甲苯基和金刚烷基）的双（亚氨基磷酰基）取代的氯化锂类胡萝卜素的合成和稳定性。它们的制备是通过相应的二硫代双（亚氨基磷酰基）乙二胺，BIPM Tol和BIPM Ad的轻度氧化来完成的，它们可以通过直接双重去质子化而容易地获得。在金刚烷基取代的体系的情况下，发现通过氯化前体的锂化的替代制备方法更具选择性。在此，氯化前体被证明是高CH酸性的。亚氨基部分的分子内去质子化导致N的形成H互变异构体，以碳负离子中心为最稳定的异构体。所制备的类胡萝卜素在室温下在固态下是稳定的。然而，在溶液中发现稳定性取决于结合在亚胺氮原子上的取代基。这样，甲苯基取代的体系在醚和烃溶剂中相当稳定，因此允许结晶。相反，金刚烷基衍生物在室温下在醚溶剂中表现出有限的稳定性。分解导致LiCl消除，亚氨基部分转移到类胡萝卜素碳原子上。
• Reactions of bis(iminophosphoranyl)methanes with chloro-bridged rhodium or iridium dimers giving complexes in which the ligand is coordinated either as a σ-N,σ-N′ or as a σ-N, σ-C chelate. X-ray crystal structure of the σ-N, σ-N′ Rh(I) complex Rh{(4-CH3-C6H4-NPPh2)2CH2}(COD)]PF6
  作者：Pieter Imhoff、Rob van Asselt、Cornelis J. Elsevier、Martin C. Zoutberg、Casper H. Stam

  DOI：10.1016/s0020-1693(00)83048-0

  日期：1991.6

  observed reflections converged to R = 0.087. The structure comprises a distorted square planar Rh(I) environment where the coordination positions are taken by COD and the two nitrogen atoms of the bipm ligand. The six-membered RhNPCPNRh metallacycle has a distorted boat conformation. Synthesis and spectroscopic data of the pure complexes II and III are described. The formation of the complexes and

  [ML 2 CI] 2（MRh，Ir; L 2COD，NBD;LCO）与双亚氨基磷酰基甲烷CH 2（PPh 2NR）2（bipm，I）的桥拆分反应导致具有N，N'和N，C二齿配位bipm的Rh（I）和Ir（I）络合物：[ML 2 （4-R'-C 6 H 4-NPPh2）2 CH 2}] + X-（II）和[ML 2 （4-R'- C 6 H 4 -NH-PPh 2）CH（PPh 2NC6 H 4 -R'-4）}] + X-（III; R′＝ CH 3，NO 2 OCH 3； X ＝ Cl，MCl 2 L 2，BF 4，PF 6）。II：III的比例取决于金属，bipm配体I，溶剂和银（I）或钠盐的存在。在N，C配位的bipm中，发生了从碳到侧氮原子的1,3-H互变异构转变。解析了[Rh （4-CH 3 -C 6 H 4 -N 2PPh 2）2 CH 2}（COD）] PF
• Preparation and crystal structure of [HPPh2NH-p-tolyl)]-[Rh(COD)Cl2]. A rhodium(I) complex containing a new σ-N,σ-C-chelating iminophosphoranylmethanide ligand
  作者：P. Imhoff、C.J. Elsevier

  DOI：10.1016/0022-328x(89)87016-0

  日期：1989.2

  yields two different types of compounds. In one of these the bis(iminophosphoranyl)methane ligand is coordinated in a σ-N,σ-N′-chelating mode to form a six-membered metallaheterocycle, whereas in the other the ligand is coordinated in a σ-N,σ-C-chelating mode to form a novel four-membered ring. The solid state structure of [HPPh2NH-p-tolyl)]-[Rh(COD)Cl2] has been determined by an X-ray diffraction study

  双（iminophosphoranyl）甲烷的反应[（p甲苯基- NPPh 2）2 CH 2 ]与[RHL 2 CL] 2（L = CO或L 2 = COD）产生两种不同类型的化合物。在其中一个中，双（亚氨基正膦烷基）甲烷配体以σ- N，σ- N'-螯合模式配位形成六元金属杂环，而在另一个配体中以σ- N，σ-配位。C-螯合模式形成新颖的四元环。[ HPPh 2 NH- p - tolyl ）]-[Rh（COD）Cl 2的固态结构通过X射线衍射研究确定。锂化的衍生物[（对甲苯基-NPPh 2）2 CHLi]产生一种有机铑化合物，其中双（亚氨基膦酰基）甲烷化物配体以相对于铑（I）的σ- N，σ- C-配位方式配位。
• Probing the donor strength of yldiide ligands: synthesis, structure and reactivity of rhodium complexes with a PC_ylideN pincer ligand
  作者：Sébastien Lapointe、Prakash Duari、Viktoria H. Gessner

  DOI：10.1039/d2sc06759e

  日期：——

  the metal ligand interaction by changes in the ligand protonation state is vital to many catalytic transformations based on metal–ligand cooperativity. Herein, we report on the coordination chemistry of a new PCy(H)N pincer ligand with a central ylide as donor site, which through deprotonation to the corresponding yldiide changes from a neutral L3-type ligand to an anionic L2X-type PCYN ligand. The isolation

  通过改变配体质子化状态来控制金属配体相互作用对于许多基于金属-配体协同作用的催化转化至关重要。在此，我们报告了一种新的 PC y (H)N 钳形配体与中心叶立德作为供体位点的配位化学，它通过去质子化为相应的叶立德，从中性 L 3型配体变为阴离子 L 2 X- PC Y N 型配体。一系列铑配合物的分离表明，中性叶立德 PC Y (H)N 的强供体能力在去质子化后进一步增加，复合物 [(PC Y N)Rh中报告的最低 CO 伸缩频率之一证明了这一点(CO)] ( 2) 与其他已知的铑羰基配合物相比。DFT 计算表明，高供体能力主要来自叶立德的 p π轨道与铑的 d xz轨道的反键相互作用，这增强了 CO 配体的 π* 轨道的反捐赠。这种独特的相互作用导致相当长的金属-碳键，但仍然强烈激活 CO 配体，以最大限度地减少铑填充轨道和叶立德配体之间的排斥力。因此，通过膦置换 CO 会导致类似膦络合物
• Selective Formation of Four-Membered Metallacyclic Pt-N-P-C Compounds from Reactions of Bis((N-arylimino)phosphoranyl)methanes with Halide-Bridged Platinum(II) Phosphine Dimers. X-ray Crystal Structures of [PtCl(PMe2Ph){CH(PPh2:NC6H4-4-CH3)(PPh2N'HC6H4-4-CH3)}]+Cl- and [PtCl(PEt3){CH(PPh2:NC6H4-4-CH3)(PPh2N'HC6H4-4-CH3)}]+[PtCl3(PEt3)]-
  作者：Mandy W. Avis、Kees Vrieze、Huub Kooijman、Nora Veldman、Anthony L. Spek、Cornelis J. Elsevier

  DOI：10.1021/ic00120a013

  日期：1995.8

  Bridge-splitting reactions of Pt(2)X(4)(PR(3))(2) (X = Cl, Br; PR(3) = PEt(3), PMe(2)Ph) with bis(iminophosphoranyl)methanes CH2(PPh(2)=NC6H4-4-R')(2) (BIPM: 1a, R' = Me; 1b, R' = OMe) produced Pt(II) complexes, in which the BIPM ligand is N,C-coordinated: [PtX(PR(3))CH-(PPh(2)=N-C6H4-4-R') (PPh(2)-NH-C6H4-4-R')}]Y-+(-) (2a-f, R' = CH3, OCH3, Y = Cl, Br, BF4, CF3CO2; 2g, R' = CH3, PR(3) = PEt(3), Y = PtCl(3)PEt(3)). In the N,C-coordinated BIPM, a net 1,3-H-shift from the bridging methylene group to the noncoordinated N-atom has taken place. NMR studies have revealed a monodentate sigma-N-coordinated species PtX(2)(PR(3))N(C6H4-4-R')=PPh(2)CH(2)PPh(2)=NC6H4 A, as the first intermediate in the formation of 2. The complex formation is strongly dependent on the metal to ligand ratio, M:L. For M:L = 2:1, compound 2g(i) was formed, a N,N'-coordinated six-membered platinacycle, followed by conversion into the N,C chelate 2g, whereas at M:L = 1:2 two new products were obtained; a deprotonated Pt(II) complex with N,C-coordinated BIPM, [PtX(PR(3))CH(PPh(2)=NC6H4-4-R')(2)] (3; X = Cl, PR(3) = PEt(3), R' = CH3), and the HCl salt of the ligand [HC(PPh(2)NHC(6)H(4)-4-R')(2)]Cl-+(-) (4). The molecular structures of [PtCl(PMe(2)Ph)CH(PPh(2)=NC6H4-4-CH3)(PPh(2)N'HC6H4-4-CH3)}](+)(Cl)(-) (2d) and [PtCl(PEt(3))CH(PPh(2)=NC6H4-4-CH3)(PPh(2)N'HC6H4-4-CH3)}](+)(PtCl(3)PEt(3))(-) (2g) have been determined by X-ray crystallography. Crystal data for 2d: trigonal, space group P $($) over bar$$ 1, with a = 14.3852(11) Angstrom, b = 15.4886(9) Angstrom, c = 20.190(2) Angstrom, alpha = 100.580(7)degrees, beta = 92.223(8)degrees, gamma = 99.508(6)degrees, V = 4350.1(6) Angstrom(3), and Z = 4. Crystal data for 2g: trigonal, space group Pi, with a = 10.1970(8) Angstrom, b = 14.5045(9) Angstrom, c = 20.5471(19) Angstrom, alpha = 96.154(7)degrees, beta = 103.993(7)degrees, gamma 107.548(6)degrees, V = 2757.8(4) Angstrom(3), and Z = 2. The structure refinement converged to R(w) = 0.0432, R = 0.0436 for 2d and wR2 = 0.1247, R1 = 0.501 for 2g. The structure of the cationic parts of 2d and 2g comprises a distorted square planar Pt(II) environment, the coordination sites taken by PR(3), Cl, and the N and C atoms of the BIPM ligand. The structure of the anionic part of 2g, PtCl3(PEt(3)), is almost perfectly square-planar and is linked with the cationic part via a NH...Cl hydrogen bond.