Tl[PhB(CH2P(i)Pr2)3] | 579444-61-4

• 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: Tl[PhB(CH2P(i)Pr2)3]
• 英文别名: thallium(1+);tris[di(propan-2-yl)phosphanylmethyl]-phenylboranuide
• CAS: 579444-61-4
• 化学式: C₂₇H₅₃BP₃*Tl
• 分子量: 685.833
• InChiKey: QUSDOANLVTZQMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.48
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Tl[PhB(CH2P(i)Pr2)3] 在 n-butyllithium 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 生成 [κ2-PhB(CH2PiPr2)3]Ni(2,3:5,6-dibenzo-7-azabicyclo[2.2.1]-hepta-2,5-diene(1-))
  参考文献：
  名称：

  “ [BP3] NiX”平台的配位化学：以低价镍为目标，有望成为L3Ni = E和L3Ni（三键）E键的候选物。

  摘要：

  由释放电子的单阴离子三（膦）硼酸酯配体[PhBP3]和[PhBPiPr3]（[PhBP3] = [PhB（CH2PPh2）3]-，[PhBPiPr3] = [PhB（CH2PiPr2）3]-）已合成，以探讨其配位化学的基本方面。伪四面体二价卤化物配合物[PhBP3] NiCl（1），[PhBP3] NiI（2）和[PhBPiPr3] NiCl（3）是通过[PhBP3] Tl或[PhBPiPr3] Tl与（Ph3P）2NiCl2的金属化制备的，NiI2和（DME）NiCl2（DME = 1,2-二甲氧基乙烷）。配合物1是可通过取代反应访问的一系列配合物的多用途前体，包括[PhBP3] Ni（N3）（4），[PhBP3] Ni（OSiPh3）（5），[PhBP3] Ni（Op-tBu-Ph）（ 6）和[PhBP3] Ni（Sp-tBu-Ph）（7）。配合物2-5和7已经通过X射线衍射（XRD）

  DOI：

  10.1021/ic049936p
• 作为产物：
  描述：

  thallium(I) hexafluorophosphate 、 lithium,methanidyl-di(propan-2-yl)phosphane 、 二氯苯酚溴酯 在 TMEDA 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以58%的产率得到Tl[PhB(CH2P(i)Pr2)3]
  参考文献：
  名称：

  The Strong-Field Tripodal Phosphine Donor, [PhB(CH₂PⁱPr₂)₃]^-, Provides Access to Electronically and Coordinatively Unsaturated Transition Metal Complexes

  摘要：

  This paper introduces a sterically encumbered, strong-field tris(diisopropylphosphino)borate ligand, [PhBp(3)(iPr)] ([PhBP3iPr] = [PhB((CH2PPr2)-Pr-i)(3)](-)), to probe aspects of its conformational and electronic characteristics within a host of complexes. To this end, the TI(I) complex, [PhBP3iPr]TI (1), was synthesized and characterized in the solid-state by X-ray diffraction analysis. This precursor proves to be an effective transmetallating agent, as evidenced by its reaction with the divalent halides FeCl2 and CoX2 (X = Cl, 1) to produce the monomeric, 4-coordinate, high-spin derivatives [PhBP3iPr]FeCl (2) and [PhBP3iPr]CoX (X = Cl (3), 1 (4)) in good yield. Complexes 2-4 were each characterized by X-ray diffraction analysis and shown to be monomeric in the solid-state. For conformational and electronic comparison within a system exhibiting higher than 4-coordination, the 16-electron ruthenium complexes {[PhBP3iPr]Ru(mu-Cl)}(2) (5) and {[PhBP3]Ru(mu-Cl)}(2) (6) were prepared and characterized ([PhBP3] = [PhB(CH2PPh2)(3)](-)). The chloride complexes 2 and 3 reacted with excess CO to afford the divalent, monocarbonyl adducts [PhBP3iPr]- FeCl(CO) (7) and [PhBP3iPr]CoCl(CO) (8), respectively. Reaction of 4 with excess CO resulted in the monovalent, dicarbonyl product [PhBP3iPr]Co-I(CO)(2) (9). Complexes 5 and 6 also bound CO readily, providing the octahedral, 18-electron complexes [PhBP3iPr]RuCl(CO)(2) (10) and [PhBP3]RuCl(CO)(2) (11), respectively. Dimers 5 and 6 were broken up by reaction with trimethylphosphine to produce the mono-PMe3 adducts [PhBP3iPr]RuCl(PMe3) (12) and [PhBP3]RuCl(PMe3) (13). Stoichiometric oxidation of 3 with dioxygen provided the 4-electron oxidation product [PhB(CH2P(O)Pr-i(2))(2)((CH2PPr2)-Pr-i)]CoCl (14), while exposure of 3 to excess oxygen results in the 6-electron oxidation product [PhB(CH2P(O)Pr-i(2))(3)]CoCl (15). Complexes 2 and 4 were characterized via cyclic voltammetry to compare their redox behavior to their [PhBP3] analogues. Complex 4 was also studied by SQUID magnetization and EPR spectroscopy to confirm its high-spin assignment, providing an interesting contrast to its previously described low-spin relative, [PhBP3]CoI. The difference in spin states observed for these two systems reflects the conformational rigidity of the [PhBp(3)(iPr)] ligand by comparison to [PhBP3], leaving the former less able to accommodate a JT-distorted electronic ground state

  DOI：

  10.1021/ic0343096

文献信息

• Pseudotetrahedral Manganese Complexes Supported by the Anionic Tris(phosphino)borate Ligand [PhBP<i>ⁱ</i>^Pr₃]
  作者：Connie C. Lu、Jonas C. Peters

  DOI：10.1021/ic060735q

  日期：2006.10.1

  presents aspects of the coordination chemistry of mono- and divalent manganese complexes supported by the anionic tris(phosphino)borate ligand, [PhBP(i)(Pr)3] (where [PhBP(i)(Pr)3] = [PhB(CH(2)P(i)Pr2)3]-). The Mn(II) halide complexes, [PhBP(i)(Pr)3]MnCl (1) and [PhBP(i)(Pr)3]MnI (2), have been characterized by X-ray diffraction, SQUID magnetometry, and EPR spectroscopy. Compound 2 serves as a precursor

  本文介绍了由阴离子三（膦）硼酸酯配体[PhBP（i）（Pr）3]（其中[PhBP（i）（Pr）3] = [ PhB（CH（2）P（i）Pr2）3]-）。Mn（II）卤化物络合物[PhBP（i）（Pr）3] MnCl（1）和[PhBP（i）（Pr）3] MnI（2）已通过X射线衍射，SQUID磁力分析进行了表征，和EPR光谱。化合物2充当一系列叠氮化锰，烷基和酰胺物种的前体：[PhBP（i）（Pr）3] Mn（N3）（3），[PhBP（i）（Pr）3] Mn（CH2Ph ）（4），[PhBP（i）（Pr）3] Mn（Me）（5），[PhBP（i）（Pr）3] Mn（NH（2,6-（i）Pr2-C6H3））（ 6），[PhBP（i）（Pr）3] Mn（dbabh）（7）和[PhBP（i）（Pr）3] Mn（1-Ph（异吲哚酸酯））（8）。配合物2-8具有二价金属中心，且为拟四面体。它们共同代表