bis[bis(2-methylphenyl)bismuth] oxide | 382148-96-1

• 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: bis[bis(2-methylphenyl)bismuth] oxide
• 英文别名: tetrakis(2-methylphenyl)dibismuth oxide；[(o-tolyl)2BiOBi(o-tolyl)2]；bis(2-methylphenyl)bismuthanyloxy-bis(2-methylphenyl)bismuthane
• CAS: 382148-96-1
• 化学式: C₂₈H₂₈Bi₂O
• 分子量: 798.491
• InChiKey: JYJPNAMFSXGKEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.85
• 重原子数：
  31.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  bis[bis(2-methylphenyl)bismuth] oxide 以 氘代氯仿 为溶剂， 生成 三邻甲苯基铋
  参考文献：
  名称：

  Diverse Structures and Remarkable Oxidizing Ability of Triarylbismuthane Oxides. Comparative Study on the Structure and Reactivity of a Series of Triarylpnictogen Oxides

  摘要：

  A systematic series of triarylbismuthane oxides was prepared in order to disclose their structure and reactivity, which have been compared with those of lighter pnictogen counterparts. X-ray crystallographic analysis of tris(2-methoxyphenyl)bismuthane oxide and tris(2-methoxyphenyl)stibane oxide revealed that they exist as dimers with a flat bis(mu-oxo) ring, implying that the polarized Bi+-O- and Sb+-O- bonds aggregate to attain electrostatic stabilization. In sharp contrast to their phosphorus, arsenic, and antimony counterparts, triarylbismuthane oxides are thermally unstable and possess a high oxidizing ability. In particular, the bismuthane oxides bearing ortho-substituted aryl ligands oxidized primary and. secondary alcohols to aldehydes and ketones, respectively, with high efficiency under mild conditions.

  DOI：

  10.1021/om0494115
• 作为产物：
  描述：

  [(trifluoroacetyl)imino]tris(2-methylphenyl)-λ5-bismuthane 在 KOC(CH₃)3 、 moisture 作用下， 以 氘代氯仿 、 二氯甲烷 、 水 为溶剂， 生成 bis[bis(2-methylphenyl)bismuth] oxide
  参考文献：
  名称：

  (酰基亚氨基)三芳基-λ5-铋烷的合成、结构和反应：(酰基亚氨基)pnictorane系列的第一次比较研究

  摘要：

  报道了（酰基亚氨基）三芳基-λ(5)-铋烷的合成、结构和反应，以及一系列（酰基亚氨基）pnictoranes 的结构和反应性的比较研究。邻位取代三芳基铋二氯化物的处理 1 (Ar(3)BiCl(2); Ar = 2-MeC(6)H(4), 2-MeOC(6)H(4), 2,4,6-Me( 3)C(6)H(2)) 与酰胺 2 (H(2)NCOR; R = CF(3), CCl(3), 3,5-(CF(3))(2)C(6) H(3)) 在二氯甲烷中 2.2 当量 KO-t-Bu 的存在下以 77-96% 的产率提供（酰基亚氨基）三芳基-λ（5）-铋烷 3（Ar(3)Bi=NCOR）。邻位取代芳基配体和吸电子 N 取代基分别为反应性 Bi=N 键提供动力学和热力学稳定性。一系列（酰基亚氨基）pnictoranes (Ar(3)M=NCOR and H(3)M=NCOCF(3); M = P, As

  DOI：

  10.1021/ja003623l

文献信息

• Reactivity and Properties of [−O−Bi^III...OMo−]<i>_n</i> Chains
  作者：Stefan Roggan、Christian Limberg、Burkhard Ziemer、Maike Siemons、Ulrich Simon

  DOI：10.1021/ic061198c

  日期：2006.10.30

  A coordination polymer [Cp*(O)(2)Mo-O-Bi(o-tolyl)(2)](n1) II, containing Mo-O-Bi and Mo=O center dot center dot center dot Bi moieties was investigated with respect to its behavior in contact with OH- and Cp2MoH2 and as potential single source precursor in the polyol method. It turned out that hydroxide as a base breaks up the polymer to yield Cp*MoO3- and (o-tolyl) 2BiOH. The latter polymerizes to give the coordination polymer [(o-tolyl)(2)BiOH](n1) 1. Alternatively, 1 can be prepared by reacting [(o-tolyl)(2)Bi(hmpa)(2)]SO3CF3 with NBu4OH/H2O in thf/water. If, however, NBu4OH/MeOH is used in dichloromethane as the solvent, the (o-tolyl)(2)BiOH formed intermediately undergoes methanolysis, and finally, [(o-tolyl)(2)BiOMe](n1) 3, is isolated. Although 1 and 3 are very similar compounds, their crystal structures differ significantly: while the structure of 1 is dominated by secondary bonding leading to seesaw-type coordination geometries around the Bi centers, the Bi atoms in 3 are coordinated in a distorted tetrahedral fashion, and secondary bonding plays only a minor role. If 1 is dissolved in a nonpolar, nonprotic solvent, condensation reactions occur immediately leading to [(o-tolyl)(2)BiOBi(o-tolyl)(2)], 2, which can be obtained on a preparative scale this way. Compound 3 which can be prepared in good yields may prove to be a useful starting material in bismuth chemistry. Here, it was shown to react with molybdocene dihydrides to provide stable Bi-substituted molybdocene monohydrides [Cp-R(2)-Mo( H)(Bi(o-tolyl)(2))] (R = Me 4, R = H 5); compounds of that type were identified in solution before but had so far eluded isolation. Compound 4, whose crystal structure is discussed, also forms when II is treated with methylated molybdocene dihydride. This obviously leads to the formation of Mo-Bi bonds (-> 4), as well as Mo-OH units, which undergo condensation reactions leading to Mo-O-Mo moieties (i.e., [Cp*2Mo2O5] is formed as a byproduct). The use of II as precursor in the polyol method successfully led to bismuthmolybdate nanoparticles (accompanied by crystallites); however, no single phase is obtained, but biphasic materials consisting of Bi2Mo2O9 and Bi2MoO6, whose ratio can be determined by the choice of the hydrolyzing reagent, are formed instead. One of these materials proved to be capable of sensing EtOH selectively at elevated temperatures.