BrC6H3(CH2PPh2)2-2,6 | 235104-95-7

• 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: BrC6H3(CH2PPh2)2-2,6
• 英文别名: 1,3-bis(diphenylphosphinomethyl)bromo-benzene；2,6-bis(diphenylphosphinomethyl)bromobenzene；1,3-(Ph2PCH2)2C6H3Br-2；2,6-bis[(diphenylphosphanyl)methyl]bromobenzene；1-Br-2,6-(ch2pph2)2-c6h3；[2-bromo-3-(diphenylphosphanylmethyl)phenyl]methyl-diphenylphosphane
• CAS: 235104-95-7
• 化学式: C₃₂H₂₇BrP₂
• 分子量: 553.418
• InChiKey: MMZFJHUANFFBBJ-UHFFFAOYSA-N

物化性质

• 沸点：
  637.8±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  35
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  BrC6H3(CH2PPh2)2-2,6 在 正丁基锂 、 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 正己烷 、 乙醚 为溶剂， 反应 10.0h， 以82%的产率得到2,6-bis[(diphenylthioxophosphanyl)methyl]benzenethiol
  参考文献：
  名称：

  Synthesis of Oxygen- and Sulfur-Bridged Dirhodium Complexes and Their Use As Catalysts in the Chemoselective Hydrogenation of Alkenes

  摘要：

  Oxygen-bridged and sulfur-bridged rhodium homobimetallic complexes were synthesized as airstable crystals by using 2,6-bis(phosphanylmethyl)phenolate and -thiophenolate as the ligands, respectively. The oxygen-bridged dirhodium complex has a symmetrical structure where the carbon atom at the ipso position, oxygen, and two rhodium atoms are located in the same plane. It is thermally stable compared to the sulfur-bridged dirhodium complex and shows catalytic activity for hydrogenation of alkenes with high chemoselectivity.

  DOI：

  10.1021/om100067r
• 作为产物：
  描述：

  2,6-二甲基溴苯 在 N-溴代丁二酰亚胺(NBS) 、 sodium 、 过氧化苯甲酰 作用下， 以 1,4-二氧六环 为溶剂， 反应 2.0h， 生成 BrC6H3(CH2PPh2)2-2,6
  参考文献：
  名称：

  An EPR study of the intramolecular dynamics in o-semiquinonic nickel complexes with a diphosphorous pincer ligandElectronic supplementary information (ESI) available: synthetic procedures. See http://www.rsc.org/suppdata/cc/b3/b308701h/

  摘要：

  具有2,6-bis(diphenylphosphinomethyl)phenyl的方锥型o-半醌镍络合物具有灵活的配位球，并在溶液中以快速的互变体混合物存在，依据EPR时间尺度，在室温下相互转化。

  DOI：

  10.1039/b308701h
• 作为试剂：
  描述：

  丁炔二醇 、 [(E)-2-苯基乙烯基]硼酸 在 palladium diacetate 溶剂黄146 、 BrC6H3(CH2PPh2)2-2,6 作用下， 以 1,4-二氧六环 为溶剂， 反应 10.0h， 以79%的产率得到
  参考文献：
  名称：

  室温下钯催化的有机硼酸与炔烃的加成反应

  摘要：

  Pd(OAc) 2 与 2-bromo-1,3-bis-[diphenylphosphenomethyl)] 苯 (1) 或 2-bromo-1,3-bis-[di-tert-butylphosphenomethyl)] 苯 (3) 催化的组合各种炔烃的加氢芳基化和加氢烯基化在反应时间和温度方面更有效。

  DOI：

  10.1055/s-2005-862362

文献信息

• EPR study of intramolecular dynamics in o-semiquinonic nickel complexes with PCP-pincer ligand in solution
  作者：Konstantin A. Kozhanov、Michael P. Bubnov、Vladimir K. Cherkasov、Georgy K. Fukin、Gleb A. Abakumov

  DOI：10.1039/b407972h

  日期：——

  A number of square pyramidal o-semiquinonic nickel complexes with 2,6-bis(diphenylphosphinomethyl)phenyl were investigated by EPR spectroscopy in solution. The complexes have flexible coordination spheres and can exist in solution as two isomers rapidly (on the EPR timescale) interconverting one to another at room temperature. The equilibrium is entropy driven and does not significantly depend on the substituents in the semiquinone ring. The spin density distribution depends on mesomeric properties and bulkiness of substituents in ortho-position to oxygen atoms.

  一系列方锥形的o-半醌镍配合物与2,6-双(二苯基膦甲基)苯进行了电子顺磁共振（EPR）光谱学研究。这些配合物具有灵活的配位球，并且在室温下可以作为两种异构体在溶液中快速（在EPR时间尺度上）相互转化。平衡是由熵驱动的，并且不显著依赖于半醌环中的取代基。自旋密度分布取决于取代基在氧原子邻位的共振性质和体积。
• Activation of Aryl Halides at Gold(I): Practical Synthesis of (P,C) Cyclometalated Gold(III) Complexes
  作者：Johannes Guenther、Sonia Mallet-Ladeira、Laura Estevez、Karinne Miqueu、Abderrahmane Amgoune、Didier Bourissou

  DOI：10.1021/ja412432k

  日期：2014.2.5

  phosphine chelation, direct evidence for oxidative addition of Csp(2)-X bonds (X = I, Br) to a single gold atom is reported. NMR studies and DFT calculations provide insight into this unprecedented transformation, which gives straightforward access to stable (P,C) cyclometalated gold(III) complexes.

  利用膦螯合，报道了 Csp(2)-X 键 (X = I, Br) 氧化加成到单个金原子上的直接证据。NMR 研究和 DFT 计算提供了对这种前所未有的转化的深入了解，从而可以直接获得稳定的 (P,C) 环金属化金 (III) 配合物。
• Complexes of Bis-<i>o</i><i>rtho</i>-cyclometalated Bisphosphinoaryl Ruthenium(II) Cations with Neutral <i>Meta</i>-bisphosphinoarene Ligands Containing an Agostic C−H···Ru Interaction
  作者：Paulo Dani、Mieke A. M. Toorneman、Gerard P. M. van Klink、Gerard van Koten

  DOI：10.1021/om0005001

  日期：2000.12.1

  The synthesis, characterization, and reactivity of various ruthenium(II) complexes [Ru(R−PCP)(R‘−PCHP)][OTf] are presented. These complexes are highly dissymmetric and show fluxional behavior in solution. They contain one monoanionic, η3-P,C,P‘-tridentate-bonded bisphosphinoaryl ligand (R−PCP = [C6H2(CH2PPh2)2-2,6-R-4]-; R = H or Br) and one neutral, trans-P,P‘-bidentate-bonded bisphosphinoarene ligand

  介绍了各种钌（II）配合物[Ru（R-PCP）（R'-PCHP）] [OTf]的合成，表征和反应性。这些络合物高度不对称，并在溶液中显示出通量行为。它们含有一个单阴离子，η 3 - P，C，P ' -tridentate键合的配体bisphosphinoaryl（R-PCP = [C 6 H ^ 2（CH 2 PPH 2）2 -2,6-R-4] - ; R = H或Br）和一个中性的反式P，P '双键双膦芳烃配体（R'-PCHP = C 6 H 3（CH 2 PPh 2）2-3,5-R'-1）。CH键即邻位到两个CH 2 PPH 2个的二齿键合的配体的取代基与金属中心（ⅰ相互作用。 ê ，具有与阳离子钌中心的agostic接触）。所述agostic质子的在位置1通过的若干两维NMR技术手段获得的1 H NMR光谱以及在溶液中的这些复合物的三维结构（1 H- 1 ħCOSY，31 P- 1 ħCOZY
• Dilworth, Jonathan R.; Zheng, Yifan; Griffiths, D. Vaughan, Journal of the Chemical Society, Dalton Transactions, 1999, # 11, p. 1877 - 1881
  作者：Dilworth, Jonathan R.、Zheng, Yifan、Griffiths, D. Vaughan

  DOI：——

  日期：——
• Synthesis of Oxygen- and Sulfur-Bridged Dirhodium Complexes and Their Use As Catalysts in the Chemoselective Hydrogenation of Alkenes
  作者：Chuan Zhu、Noriaki Yukimura、Motoki Yamane

  DOI：10.1021/om100067r

  日期：2010.5.10

  Oxygen-bridged and sulfur-bridged rhodium homobimetallic complexes were synthesized as airstable crystals by using 2,6-bis(phosphanylmethyl)phenolate and -thiophenolate as the ligands, respectively. The oxygen-bridged dirhodium complex has a symmetrical structure where the carbon atom at the ipso position, oxygen, and two rhodium atoms are located in the same plane. It is thermally stable compared to the sulfur-bridged dirhodium complex and shows catalytic activity for hydrogenation of alkenes with high chemoselectivity.