Ph2P-C2H4-B(C6F5)2 | 1003010-55-6

• 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: Ph2P-C2H4-B(C6F5)2
• 英文别名: 2,2-Bis(2,3,4,5,6-pentafluorophenyl)-1,1-bis(2,4,6-trimethylphenyl)-1-phosphonia-2-boranuidacyclobutane；2,2-bis(2,3,4,5,6-pentafluorophenyl)-1,1-bis(2,4,6-trimethylphenyl)-1-phosphonia-2-boranuidacyclobutane
• CAS: 1003010-55-6
• 化学式: C₃₂H₂₆BF₁₀P
• 分子量: 642.327
• InChiKey: GUUORXHMZQVHSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.67
• 重原子数：
  44
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  Ph2P-C2H4-B(C6F5)2 以 氘代苯 、 苯 为溶剂， 20.0~60.0 ℃ 、150.0 kPa 条件下， 反应 2.0h， 生成 2,2-dimesityl-6,6-bis(perfluorophenyl)-5-(phenyl(trimethylsilyl)methylene)-3,4,5,6-tetrahydro-1l3,2l5,6l4-oxaphosphaborinine
  参考文献：
  名称：

  Frustrated Lewis Pair Modification by 1,1-Carboboration: Disclosure of a Phosphine Oxide Triggered Nitrogen Monoxide Addition to an Intramolecular P/B Frustrated Lewis Pair

  摘要：

  The vicinal frustrated Lewis pair (FLP) mes2P-CH2CH2-B(C6F5)2 (3) reacts with phenyl(trimethylsilyl)acetylene by 1,1-carboboration to give the extended C3-bridged FLP 6 featuring a substituted vinylborane subunit. The FLP 6 actively cleaves dihydrogen. The FLP 3 also undergoes a 1,1-carboboration reaction with diphenylphosphino(trimethylsilyl)acetylene to give the P/B/P FLP 11 that features a central unsaturated four-membered heterocyclic P/B FLP and a pendant CH2CH2-Pmes2 functional group. Compound 11 reacts with nitric oxide (NO) by oxidation of the pendant Pmes2 unit to the P(O)mes2 phosphine oxide and N,N-addition of the P/B FLP unit to NO to yield the persistent P/B/PO FLPNO aminoxyl radical 14. This reaction is initiated by P(O)mes2 formation and opening of the central Ph2P···B(C6F5)2 linkage triggered by the pendant CH2CH2-P(O)mes2 group.

  DOI：

  10.1021/ja5028293
• 作为产物：
  描述：

  dimesitylvinylphosphine 、 bis(pentafluorophenyl)borane 以 正戊烷 为溶剂， 反应 1.0h， 以75%的产率得到Ph2P-C2H4-B(C6F5)2
  参考文献：
  名称：

  Rapid intramolecular heterolytic dihydrogen activation by a four-membered heterocyclic phosphane–borane adduct

  摘要：

  一个四元环状分子内磷烷硼烷加合物激活二氢，生成相应的乙烯桥键齐聚磷酸氢硼酸盐体系，从而还原苯甲醛。

  DOI：

  10.1039/b710475h

文献信息

• Anomalous Staudinger reaction at intramolecular frustrated P–B Lewis pair frameworks
  作者：Annika Stute、Lukas Heletta、Roland Fröhlich、Constantin G. Daniliuc、Gerald Kehr、Gerhard Erker

  DOI：10.1039/c2cc36782c

  日期：——

  The FLP-mesityl azide addition products 5, formed by FLP-addition to the terminal azide nitrogen atom, undergo N-N bond cleavage in an unusual variant of the Staudinger reaction upon thermolysis or photolysis to give an internally borane stabilized [P]=NH phosphinimine and a dimethylindazole derivative.

  通过将FLP加成至末端叠氮氮原子而形成的FLP-间苯二甲叠氮加成产物5在热解或光解后在Staudinger反应的不寻常变体中进行NN键裂解，得到内部硼烷稳定的[P] = NH膦亚胺和二甲基吲唑衍生物。
• The [(NHC)B(H)C₆F₅]⁺Cations and Their [B](H)−CO Borane Carbonyls
  作者：Chaohuang Chen、Jun Li、Constantin G. Daniliuc、Christian Mück‐Lichtenfeld、Gerald Kehr、Gerhard Erker

  DOI：10.1002/anie.202009353

  日期：2020.11.23

  Hydride abstraction from the heterocyclic carbene borane adducts (NHC)BH2C6F5 (NHC: IMes or IMe4) gave the B−H containing [(NHC)B(H)C6F5]+ borenium cations. They added carbon monoxide to give the respective [(NHC)B(H)(C6F5)CO]+ boron carbonyl cations. Carbon nucleophiles add to the boron carbonyl to give [B](H) acyls. Hydride reduced the [B]CO cation to hydroxymethylborane derivatives.

  从杂环卡宾硼烷加合物（NHC）BH 2 C 6 F 5（NHC：IMes或IMe 4）氢化物提取得到含[[NHC）B（H）C 6 F 5 ] +硼阳离子的BH。他们加入了一氧化碳，分别得到[（NHC）B（H）（C 6 F 5）CO] +羰基硼阳离子。碳亲核试剂加到羰基硼上，得到[B]（H）酰基。氢化物将[B] CO阳离子还原为羟甲基硼烷衍生物。
• Reversible Heterolytic Si–H Bond Activation by an Intramolecular Frustrated Lewis Pair
  作者：Wanli Nie、Hendrik F. T. Klare、Martin Oestreich、Roland Fröhlich、Gerald Kehr、Gerhard Erker

  DOI：10.5560/znb.2012-0181

  日期：2012.10.1

  The intramolecular frustrated P/B Lewis pair Mes₂PCH₂CH₂B(C₆F₅)₂ (7) reacts readily with phenylsilane by heterolytic cleavage of the Si-H bond to give the zwitterion [Mes₂(PhH₂Si)P+CH₂CH₂B-H(C₆F₅)₂] (8a), which has been fully characterized and its structure confirmed by X-ray crystal structure analysis. Variable-temperature NMR studies revealed that the reaction is reversible. Adduct 8a is the predominant species (ca. 98%) in CD₂Cl₂ solution at low temperature (193 K), whereas at ambient temperature (299 K) it exists in a ca. 7 : 3 equilibrium with unreacted 7 and PhSiH₃. Diphenylsilane reacted similarly with the frustrated Lewis pair 7, however, the equilibrium was found to favor the starting materials in the investigated temperature range.

  分子内沮合 P/B 路易斯对 Mes2PCH2CH2B(C6F5)2 (7) 很容易通过异性裂解 Si-H 键与苯基硅烷发生反应，生成齐聚物 [Mes2(PhH2Si)P+CH2CH2B-H(C6F5)2]（8a）。变温核磁共振研究表明，该反应是可逆的。在低温（193 K）下，加合物 8a 是 CD2Cl2 溶液中的主要物质（约 98%），而在环境温度（299 K）下，它与未反应的 7 和 PhSiH3 处于约 7 : 3 的平衡状态。二苯基硅烷与受挫的路易斯对 7 也发生了类似的反应，但在研究的温度范围内，发现平衡有利于起始材料。
• Addition reactions to the intramolecular mesityl2P–CH2–CH2–B(C6F5)2 frustrated Lewis pair
  作者：Cornelia M. Mömming、Gerald Kehr、Birgit Wibbeling、Roland Fröhlich、Gerhard Erker

  DOI：10.1039/c0dt00015a

  日期：——

  Hydroboration of dimesitylvinylphosphine with Piers’ borane [HB(C6F5)2] gives the ethylene-bridged intramolecular frustrated P/B Lewis pair 1. It adds pyridine, tert-butyl isocyanide or pivalonitrile to the strongly electrophilic boron center to yield the respective adducts 5–7. Compound 1 undergoes a 1,1-phosphine/borane addition to the terminal nitrogen center of phenyl azide to yield the five-membered

  硼氢化 二甲基乙烯基膦 与皮尔斯 硼烷[HB（C 6 F 5）2 ]给出乙烯桥接分子内受挫 P/ B Lewis对1。它增加了吡啶， 叔丁基异氰化物 或者 新戊腈 强烈的亲电性 硼中心产生相应的加合物5-7。化合物1经过1,1-膦/硼烷加成到化合物的末端氮中心叠氮化苯产生五元杂环8，其侧基为–N N–Ph。可以认为这是施陶丁格反应的硼稳定中间体。苯甲醛 和 异氰酸苯酯 经历 1,2-磷/乙在它们的反应性羰基上加成1，分别得到相应的六元杂环9和10。这P/ B Lewis对与 亚硝基苯通过在P–N和O–B键形成下的–N O单元上加成1,2-形成六元杂环11。化合物5 - 11通过X射线晶体结构分析进行表征。
• Frustrated Lewis Pair Modification by 1,1-Carboboration: Disclosure of a Phosphine Oxide Triggered Nitrogen Monoxide Addition to an Intramolecular P/B Frustrated Lewis Pair
  作者：René Liedtke、Felix Scheidt、Jinjun Ren、Birgitta Schirmer、Allan Jay P. Cardenas、Constantin G. Daniliuc、Hellmut Eckert、Timothy H. Warren、Stefan Grimme、Gerald Kehr、Gerhard Erker

  DOI：10.1021/ja5028293

  日期：2014.6.25

  The vicinal frustrated Lewis pair (FLP) mes2P-CH2CH2-B(C6F5)2 (3) reacts with phenyl(trimethylsilyl)acetylene by 1,1-carboboration to give the extended C3-bridged FLP 6 featuring a substituted vinylborane subunit. The FLP 6 actively cleaves dihydrogen. The FLP 3 also undergoes a 1,1-carboboration reaction with diphenylphosphino(trimethylsilyl)acetylene to give the P/B/P FLP 11 that features a central unsaturated four-membered heterocyclic P/B FLP and a pendant CH2CH2-Pmes2 functional group. Compound 11 reacts with nitric oxide (NO) by oxidation of the pendant Pmes2 unit to the P(O)mes2 phosphine oxide and N,N-addition of the P/B FLP unit to NO to yield the persistent P/B/PO FLPNO aminoxyl radical 14. This reaction is initiated by P(O)mes2 formation and opening of the central Ph2P···B(C6F5)2 linkage triggered by the pendant CH2CH2-P(O)mes2 group.