[Li(TMEDA)][(H)C(PPh2Se)2] | 1201340-24-0

• 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: [Li(TMEDA)][(H)C(PPh2Se)2]
• 英文别名: lithium;diphenylphosphinoselenoylmethylidene-diphenyl-selenido-λ5-phosphane;N,N,N',N'-tetramethylethane-1,2-diamine
• CAS: 1201340-24-0
• 化学式: C₃₁H₃₇LiN₂P₂Se₂
• 分子量: 664.457
• InChiKey: FGPKPSYIIUDPTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.36
• 重原子数：
  38
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [Li(TMEDA)][(H)C(PPh2Se)2] 、 thallium (I) ethoxide 以 甲苯 为溶剂， 以75%的产率得到Tl[HC(PPh2Se)2]*LiOEt
  参考文献：
  名称：

  Homoleptic, heteroleptic and mixed-valent thallium and indium complexes of multidentate chalcogen-centred PCP-bridged ligands

  摘要：

  [Li(TMEDA)][HC(PPh2Se)2] ([Li(TMEDA)]1)与TlOEt在1:1摩尔比下的类元反应生成了一种与LiOEt加合物的均配Tl(I)配合物Tl[HC(PPh2Se)2]·LiOEt (7)，其在温和加热(60 °C)下发生硒-质子交换，生成混合价态的Tl(I)/Tl(III)配合物{[Tl][Tl{(Se)C(PPh2Se)2}2]}∞ (8)。在2:1摩尔比下，TlOEt与[Li(TMEDA)]2[(SPh2P)2CE′E′C(PPh2S)2] (3b, E′ = S; 3c, E′ = Se)反应生成了二核Tl(I)/Tl(I)配合物Tl2[(SPh2P)2CE′E′C(PPh2S)2] (9b, E′ = S; 9c, E′ = Se)。添加[Li(TMEDA)]1至InCl3时也发生了硒-质子交换，生成异配配合物(TMEDA)InCl[(Se)C(PPh2Se)2] (10a)。这类In(III)配合物的其他例子，如(TMEDA)InCl[(E′)C(PPh2E)2] (10b, E = E′ = S; 10c, E = S, E′ = Se)，是通过InCl3与[Li(TMEDA)]2[(E′)C(PPh2E)2] (2b, E = E′ = S; 2c, E = S, E′ = Se)的类元反应获得的。所有新化合物在溶液中通过1H和31P NMR光谱进行了表征，并且通过单晶X射线晶体学确定了8、9c和10a–c的固态结构。配合物8由Tl+离子与八面体[Tl{(Se)C(PPh2Se)2}2]−阴离子弱配位形成一维聚合物。配合物9c由两个四配位的Tl+离子组成，它们分别通过S,S′,S′′,Se键合到六齿配体[(SPh2P)2CSeSeC(PPh2S)2]2−上，其中d(Se–Se) = 2.531(2) Å。在扭曲的八面体配合物10a–c中，六个配位的In(III)中心与三齿[(E′)C(PPh2E)2]2−二阴离子、一个氯离子和一个中性二齿TMEDA配体相连。

  DOI：

  10.1039/c1dt10646e

文献信息

• Identification of a Novel η²-Se₂ Bonding Mode in Cu(I) Complexes of the Dimeric Selenocarbonyl Dianions, [(EPh₂P)₂CSeSeC(PPh₂E)₂]²⁻ (E = S, Se)
  作者：Maarit Risto、Jari Konu、Tristram Chivers

  DOI：10.1021/ic101866v

  日期：2011.1.17

  A metathetical reaction between [Li(TMEDA)][(H)C(PPh2Se)(2)] and CuCl2 in a 2:1 molar ratio afforded the dimeric Cu(I) complex, Cu-2-eta(2):eta(2)-[(EPh2P)(2)CSeSeC(PPh2E)(2))} (E = Se), via a selenium-proton exchange and an internal redox process. The analogous sulfur-containing complex (E = S) was obtained by the reactions of the dianions [(Se)C(PPh2S)(2)](2-) and [(SPh2P)(2)CSeSeC(PPh2S)(2)](2-) with CU(II)) and Cu(I) halides, respectively. Structural characterization of the Cu(I) complexes reveals a unique eta(2)-Se-2 bonding mode for the generic diselenide ligand system RSe-SeR.
• Structural and Spectroscopic Studies of the PCP-Bridged Heavy Chalcogen-Centered Monoanions [HC(PPh₂E)(PPh₂)]⁻ (E = Se, Te) and [HC(PR₂E)₂]⁻ (E = Se, Te, R = Ph; E = Se, R = ^<i>i</i>Pr): Homoleptic Group 12 Complexes and One-Electron Oxidation of [HC(PR₂Se)₂]⁻
  作者：Jari Konu、Heikki M. Tuononen、Tristram Chivers

  DOI：10.1021/ic901878h

  日期：2009.12.21

  Selenium- and tellurium-containing bis(diphenylphosphinoyl)methane monoanions were prepared by oxidation of the anion [HC(PPh2)(2)](-) with elemental chalcogens. The selenium-containing isopropyl derivative was synthesized by generating [H2C((PPr2)-Pr-i)(2)] via a reaction between [H2C(PCl2)(2)] and 4 equiv of (PrMgCl)-Pr-i prior to in situ oxidation with selenium followed by deprotonation with (LiNPr2)-Pr-i. The solid-state structures of the lithium salts of the monochalcogeno anions TMEDA center dot Li[HC(PPh2E)(PPh2)] (E = Se (Li7a), E = Te (Li7b)) and the dichalcogeno anions TMEDA center dot Li[HC-(PR2Se)(2)] (R=Ph (Li8a), Pr-i (Li8c)) revealed five- and six-membered LiEPCP and LiSePCPSe rings, respectively. The homoleptic group 12 complexes M[HC(PPh2Se)(2)](2)} (M=Zn (9a), Hg (9b)) were prepared from Li8a and MCl2 and shown to have distorted-tetrahedral structures; the nonplanarity of the carbon center in the PC(H)P unit of the Zn complex 9a is attributed to crystal-packing effects. The complexes Li7a, Li7b, Li8a, TMEDA center dot Li[HC(PPh2Te)(2)] (Li8b), Li8c, 9a, and 9b were characterized in solution by multinuclear (H-1, Li-7, C-13, P-31, Se-77, Te-125, and Hg-199) NMR spectroscopy. One-electron oxidation of Li8a and Li8c with iodine in a variety of organic solvents produced [H2C(PR2Se)(2)] (R=Pr-i, Ph) as the final product, presumably owing to hydrogen abstraction from the solvent. DFT calculations revealed a significant contribution from the p orbital on carbon to the SOMO of the radicals [HC(PR2Se)(2)](center dot) (R=Pr-i, Ph).