crown-P2 | 128496-90-2

• 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: crown-P2
• CAS: 128496-90-2
• 化学式: C₃₈H₄₈N₂O₄P₂
• 分子量: 658.758
• InChiKey: YTBVVHQTWBZGBI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.85
• 重原子数：
  46.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  43.4
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  chlorodicarbonyl(p-toluidine)iridium 、 crown-P2 以 甲苯 为溶剂， 以77%的产率得到
  参考文献：
  名称：

  Studies of thallium-iridium bonding

  摘要：

  New examples of complexes with Tl-Ir bonds have been prepared and structurally characterized. Treatment of Ph2PCH2N{(CH2)2O(CH2)2O(CH2)2}2NCH2PPh2, crown-P2, with Ir(CO)2Cl(p-toluidine) yields yellow (crown-P2)Ir(CO)Cl which reacts with thallium(I) nitrate to give yellow-orange crystals of [Tl(crown-P2)Ir(CO)Cl](NO3).CH2Cl2. These form in the triclinic space group P1BAR (No. 2) with a = 11.350 (4) angstrom, b = 13.519 (4) angstrom, c = 15.022 (4) angstrom, alpha = 97.64 (2)-degrees, beta = 101.20 (3)-degrees, gamma = 93.63 (3)-degrees at 130 K with Z = 2. Refinement of 6298 reflections and 243 parameters yielded R = 0.070, R(w) = 0.078. The complex consists of a nearly planar Ir(CO)CIP2 unit and a thallium ion within the aza-crown portion. The Tl-Ir distance is 2.875 (1) angstrom. The presence of the thallium ion perturbs the electronic spectrum of the IrP2(CO)Cl chromophore. The Tl-Ir complex has absorbance at 400 nm (epsilon = 17700) and 500 nm (epsilon = 452) at 23-degrees-C in dichloromethane and strong emission at 580 nm in frozen dichloromethane at 77 K which is not observed when the sample is warmed to 23-degrees-C. This Tl-Ir complex undergoes oxidative addition of iodine or chlorine (from iodobenzene dichloride) to form [ITl(crown-P2)Ir(CO)ClI]NO3 or [ClTl(crown-P2)Ir(CO)Cl2](NO3). These show significant increases in nu(CO) and 2J(Tl,P) that are consistent with oxidation. As a model for the formation of these oxidation products which should have Tl-Ir single bonds, the structure of (CH3CO2)2Tl(mu-O2CCH3)Ir(CO)(PPh3)2(O2CCH3).CHCl3 has been determined. Colorless crystals form in the monoclinic space group P2(1)/c (No. 14) with a = 10.815 (3) angstrom, b = 22.909 (8) angstrom, c = 21.582 (7) angstrom, beta = 118.63 (2)-degrees at 130 K with Z = 4. Refinement of 3961 reflections with 296 parameters yielded R = 0.063, R(w) = 0.059. The structure has a short Tl-Ir bond (2.611 (1) angstrom) with an acetate ion bridging the Tl-Ir unit. Two chelating acetate ligands are bound to the thallium while a terminal monodentate acetate is bound to iridium, whose coordination sphere is completed by a terminal carbonyl group and the pair of trans triphenylphosphine ligands. Thus all three common modes of acetate coordination are present in one compound. These structures are compared to that of Ir2(TlNO3)(CO)2Cl2(mu-Ph2PCH2As(Ph)CH2PPh2)2. The thallium atoms in these complexes show considerable variation in coordination number and angular ligand distribution, while the iridium atoms have rectilinear coordination. The bonding within the Tl-Ir units is discussed.

  DOI：

  10.1021/ja00008a030
• 作为产物：
  描述：

  聚合甲醛 、 二氮杂18-冠醚-6 、 二苯基膦 以 甲苯 为溶剂， 以86%的产率得到crown-P2
  参考文献：
  名称：

  Solubilizing the thallium-platinum unit of Tl2Pt(CN)4. Preparation and use of a new crown ether/phosphine hybrid ligand for linking main-group and transition-metal ions

  摘要：

  DOI：

  10.1021/ja00172a046

文献信息

• Balch, Alan L.; Fung, Ella Y.; Nagle, Jeffrey K., Inorganic Chemistry, 1993, vol. 32, # 15, p. 3295 - 3299
  作者：Balch, Alan L.、Fung, Ella Y.、Nagle, Jeffrey K.、Olmstead, Marilyn M.、Rowley, Stephen P.

  DOI：——

  日期：——
• Palladium-thallium interactions in dinuclear complexes with structural components that place the two metal centers in close proximity
  作者：Alan L. Balch、Brian J. Davis、Ella Y. Fung、Marilyn M. Olmstead

  DOI：10.1016/s0020-1693(00)92320-x

  日期：1993.10

  Structural studies on two heterodinuclear complexes containing palladium and thallium are reported and compare to complexes containing platinum/thallium and iridium/thallium combinations. [Tl(crown-P2)Pd(CN)2](PF6) . CHCl3 contains a planar P2Pd(CN)2 unit which is capped by a thallium(I) ion that is encapsulated within the azacrown portion of the crown-P2 ligand (Ph2PCH2N(CH2)2O(CH2)2O(CH2)2}2NCH2PPh2). The Pd(II)-Tl(I) distance is 2.897(2) angstrom and a qualitative molecular orbital interpretation of the bonding interaction between the d8 and s2 ions is given. Orange Pd(mu-O2CMe)4Tl(O2CMe) has a structure with four bridging acetates and one acetate ion that is chelated to the thallium. The Pd(II)/Tl(III) distance (2.702(1) angstrom) is shorter than that in the crown-P2 bridged Pd(II)-Tl(I) complex, but comparison between the two structures suggests that there is no metal-metal bond in the acetate bridged structure.