1,1-bis((N-p-tolylimino)diphenylphosphoranyl)ethane | 174157-31-4

• 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: 1,1-bis((N-p-tolylimino)diphenylphosphoranyl)ethane
• 英文别名: 1,1-bis(N-p-tolyliminodiphenylphosphoranyl)ethane；(4-Methylphenyl)imino-[1-[(4-methylphenyl)imino-diphenyl-lambda5-phosphanyl]ethyl]-diphenyl-lambda5-phosphane；(4-methylphenyl)imino-[1-[(4-methylphenyl)imino-diphenyl-λ5-phosphanyl]ethyl]-diphenyl-λ5-phosphane
• CAS: 174157-31-4
• 化学式: C₄₀H₃₈N₂P₂
• 分子量: 608.703
• InChiKey: QNIDIPUTUNOTTJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.8
• 重原子数：
  44
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  1,1-bis((N-p-tolylimino)diphenylphosphoranyl)ethane 以 二氯甲烷 为溶剂， 生成 [PtCl(PMe2Ph)(1,1-bis((N-p-tolylimino)diphenylphosphoranyl)ethane-σN,σN')](+)[Cl](-)
  参考文献：
  名称：

  Monodentate σ-N and Bidentate σ-N,σ-N‘ Coordination of 1,1-Bis((N-p-tolylimino)diphenylphosphoranyl)ethane, CHCH₃(PPh₂NC₆H₄-4-CH₃)₂, to Platinum(II)

  摘要：

  The new ligand, 1,1-bis((N-p-tolylimino)diphenylphosphoranyl)ethane (1,1-BIPE), 1, has been synthesized by means of a Staudinger reaction of 1,1-bis(diphenylphosphino)ethane (1,1-dppe) with 2 equiv of p-tolylazide. Bridge-splitting reactions of Pt2Cl4(PR(3))(2) with 1 readily afforded sigma-N monodentate complexes, [PtCl2(PR(3)){1,1-BIPE-sigma N}] (2a, PR(3) = PEt(3); 2b, PR(3) = PMe(2)Ph). Conversion of 2 into the six-membered platinacycle [PtCl(PR(3)){1,1-BIPE-sigma N,sigma N '}](+)[X](-) (3) (X = Cl, PtCl3(PR(3)), BF4) took place after prolonged stirring, its reaction rate being strongly dependent on the type of phosphine (>5 days for 2a in the presence of NaBF4, 1 h for 2b) and the metal-to-ligand ratio. The compounds 1, 2, and 3 have been fully characterized by H-1, P-31{H-1}, and C-13{H-1} NMR and IR spectroscopy, elemental analysis, or FAB mass spectroscopy. The molecular structures of CHCH3- (PPh(2)=NC6H4-4-CH3)(2) (1) and [PtCl(PMe(2)Ph){(N(pTol)=PPh(2))(2)CHCH3}](+)[Cl](-) (3b) have been determined by X-ray crystallography. Crystal data for 1: space group P2(1)/c with a = 8.9591(5) Angstrom, b = 19.1961(12) Angstrom, c = 21.9740(9) Angstrom, beta = 105.069(4)degrees, V = 3649.1(3) Angstrom(3), and Z = 4. The structure refinement converged to R = 0.080 and R(w) = 0.109. Crystal data for 3b: monoclinic, space group P2(1)/c with a 12.4021(7) Angstrom, b = 16.9705(11) Angstrom, c = 23.760(2) Angstrom, beta = 109.544(5)degrees, V = 4712.7(5) Angstrom(3), and Z = 4. The structure refinement converged to R1 = 0.057, wR2 = 0.122. Variable temperature NMR spectroscopy has revealed that complexes 3 exclusively adopt a twisted boat conformation with the methyl group in equatorial position at low temperature, in agreement with the solid state structure of 3b as determined by X-ray crystallography. Boat-to-boat inversion is assumed to take place at temperatures above 293 K. Furthermore, for 3, hindered rotation of one of the p-tolyl substituents on nitrogen has been established at low temperatures.

  DOI：

  10.1021/ic950748w

文献信息

• Reactions of bis(iminophosphoranes) with palladium(II) dichloride: Metal-induced tautomerization orthopalladation and unexpected platinum-assisted [2 + 2] cycloaddition of an aryl-nitrile with a phosphinimine moiety
  作者：Mandy W. Avis、Milko E. van der Boom、Cornelis J. Elsevier、Wilberth J.J. Smeets、Anthony L. Spek

  DOI：10.1016/s0022-328x(96)06684-3

  日期：1997.1

  Reactions of bis(iminophosphoranyl)methane, CH2(PPh(2)=N-aryl)(2), (BIPM; 1a, b) or 1, 1-bis(iminophosphoranyl)ethane (1, 1-BIPE; Ic) with Pd- and Pt-dichlorides containing weakly coordinating ligands (L) such as nitriles or cyclo-octadiene, afforded several products depending on the reaction time, type of ligand (la-c) or nature of the metal. The first reaction observed is a metal-assisted tautomerization of BIPM to aryl-N=PPh(2)-CH=PPh(2)-NH-aryl. When BIPM reacts with PdCl2(L)(2), exclusive formation of the C, N-chelate PdCl2CH(PPh(2)=N-aryl)(PPh(2)-NH-aryl)} (2a, b) is observed, whereas with 1, 1-BIPE(1c) a product mixture consisting of a C, N-chelate (2c) and an N, N'-chelate (3) is found. Orthometallation of the four-membered palladacycle (2) took place upon heating, giving the five-membered palladacycle [PdCl2(2-C6H4-PPh(NHI-pTol)-C'H-PPh(2)(NH-pTol)}-C, C'] (4). The molecular structure of 4 has been determined by X-ray crystallography, Reactions of BIPM (1a, b) with PtCl2(RC=N)(2) (R = phenyl, p-tolyl) afforded entirely different products: the six-membered platinacycles [PtCl(RC=N)aryl-N=C(R)-N=PPh(2)-CH=PPb2-NH-aryl}-C, N]Cl (5) and [PtCl2aryl-N=C(R)-N=PPh(2)-CH=PPh(2)-NH-aryl}-C, N] (6), due to an unexpected 2 + 2 cycloaddition of a nitrile with a P=N group.