Bi(o-PPh20C6H4)2Cl | 1380316-53-9

• 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: Bi(o-PPh20C6H4)2Cl
• 英文别名: [2-[Chloro-(2-diphenylphosphanylphenyl)bismuthanyl]phenyl]-diphenylphosphane
• CAS: 1380316-53-9
• 化学式: C₃₆H₂₈BiClP₂
• 分子量: 766.999
• InChiKey: NSIHCZVXRMLIEL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.55
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Bi(o-PPh20C6H4)2Cl 以 四氢呋喃 、 甲苯 为溶剂， 反应 17.0h， 生成
  参考文献：
  名称：

  铂，钯和铱的PBiP钳式配合物，具有通过氧化卤化铋-卤键合成的金属-金属键

  摘要：

  The compound BiCl(o-PPh2-C6H4)(2), PBiP-Cl, which in previous work had been shown to form complexes with pronounced M-->Bi character, when metal(I) ions of group 11 or Pt-II and Pd-II ions were coordinated, behave differently in contact with late metal atoms in low oxidation states, known to easily undergo oxidative additions: Treatment of PBiP-Cl with M(PPh3)(4), with M = Pt, Pd, led to the formal insertion of M into the Bi-Cl bond to yield complexes [MCl(PBiP)]. Analogues PBiP-X with X = Br, I that could be accessed behaved similarly, producing [MX(PBiP)]. Both types of complexation reactions-coordination of PBiP-CI as an ambiphilic ligand and oxidative addition-were observed to occur when [Ir(acac)(cod)] was chosen as the precursor compound. NMR investigations clearly indicated the presence of [Ir-III(acac)(PBiP-Cl)] and [Ir-III(acac)Cl(PBiP)] beside each other in solution, from which, however, only [Ir-III(acac)Cl(PBiP)] could be crystallized. DFT results showed that both products differ only slightly in energy. Reaction of PBiP-Cl with [Ir(acac-F-6)(cod)] led only to the iridium(III) product, underlining that electronic effects sensitively influence the course of reactivity and the position of the equilibrium.

  DOI：

  10.1021/acs.organomet.5b00439
• 作为产物：
  描述：

  氯化铋 、 (2-溴苯基)二苯基膦 在 nBuLi 作用下， 生成 Bi(o-PPh20C6H4)2Cl
  参考文献：
  名称：

  两性PBiP夹钳配体支持的金-和铂-铋-供体-受体相互作用

  摘要：

  贵金属遇上了重量级：钳形配体将铋与金和铂结合在一起，从而建立了亲金属相互作用。根据DFT计算，这些相互作用包含了主要的金属→铋元素。

  DOI：

  10.1002/anie.201200848

文献信息

• Coordination of noble metals by an ambiphilic PBiP pincer ligand: Metallophilic Bi–Cu and Bi–Ag interactions
  作者：Carolin Tschersich、Beatrice Braun、Christian Herwig、Christian Limberg

  DOI：10.1016/j.jorganchem.2014.09.019

  日期：2015.5

  the pincer ligand PBiP with MCl (M = Cu, Ag) led to the complexes [M(μ-Cl)(PBiP)]2 featuring M⋯Bi interactions, which were shown by DFT/NBO to have predominantly Bi → M character. In the series of compounds [Cu(μ-Cl)(PBiP)]2, [Ag(μ-Cl)(PBiP)]2 and [AuCl(PBiP)] the ratios between the M–Bi distances and the covalent/van der Waals radii decrease, which indicates a strengthening of the interactions. Employing

  钳位配体PBiP与MCl（M = Cu，Ag）的反应导致形成具有M⋯Bi相互作用的复合物[M（μ-Cl）（PBiP）] 2，DFT / NBO显示主要是Bi→M特点。在一系列化合物[Cu（μ-Cl）（PBiP）] 2，[Ag（μ-Cl）（PBiP）] 2和[AuCl（PBiP）]中，M–Bi距离与共价/ van之间的比率der Waals半径减小，表明相互作用增强。根据NMR光谱结果，使用具有弱相互作用阴离子的金属前驱物会生成单体配合物，但在结晶过程中会聚合形成[M（阴离子）（PBiP）] x。
• The Effect of Substituents at Lewis Acidic Bismuth(III) Centers on Its Propensity to Bind a Noble Metal Donor
  作者：Carolin Tschersich、Santina Hoof、Nicolas Frank、Christian Herwig、Christian Limberg

  DOI：10.1021/acs.inorgchem.5b02740

  日期：2016.2.15

  ambiphilic compounds BiX(o-PPh2-C6H4)2, PBiP-X, on metallophilic Pt–Bi interactions in its PtCl2 complexes two new derivatives PBiP-Me and PBiP-C6F5 were synthesized. Reaction with dichloro(1,5-cyclooctadiene)platinum(II) led to the platinum(II) complexes [PtCl2(PBiP-Me)], 3, and [PtCl2(PBiP-C6F5)], 4, which together with the halide [PtCl2(PBiP-Cl)], 2, reported previously, establish a series of related

  要研究含氟化合物BiX（o -PPh 2 -C 6 H 4）2，PBiP-X中X对其PtCl 2络合物中嗜金属Pt-Bi相互作用的影响，两种新的衍生物PBiP-Me和PBiP-C 6 F合成了5个。与二氯（1,5-环辛二烯）铂（II）反应生成铂（II）配合物[PtCl 2（PBiP-Me）]，3和[PtCl 2（PBiP-C 6 F 5）]，4，连同卤化物[PtCl 2（PBiP-Cl）]，2，以前报道的方法，建立了一系列仅在X上不同的相关PBiP-X络合物。这可以通过2与AgOTf的反应获得[PtCl 2（PBiP-OTf）] 5来补充。这些复合物的几何结构和电子结构的分析表明，在所有情况下，铂（II）中心（通过其充满d作为供体Z ^ 2个轨道）的铋（III）中心（拥有σ*（双X）/ 6p受体轨道）。这些相互作用的强度随着X的吸电子特性的增加而增加，这支持了构造这类新化合物的概念方法。