MesB(o-PPh2C6H4)2 | 1364266-41-0

• 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: MesB(o-PPh2C6H4)2
• 英文别名: [2-[(2-Diphenylphosphanylphenyl)-(2,4,6-trimethylphenyl)boranyl]phenyl]-diphenylphosphane；[2-[(2-diphenylphosphanylphenyl)-(2,4,6-trimethylphenyl)boranyl]phenyl]-diphenylphosphane
• CAS: 1364266-41-0
• 化学式: C₄₅H₃₉BP₂
• 分子量: 652.563
• InChiKey: SRPAWUDNSITQLM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.64
• 重原子数：
  48
• 可旋转键数：
  9
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  MesB(o-PPh2C6H4)2 在 sodium amalgam 作用下， 以 四氢呋喃 、 氘代苯 为溶剂， 生成 NiHC₆H₂(CH₃)3BH(C₆H₄P(C₆H₅)2)2
  参考文献：
  名称：

  Reversible H₂ Addition across a Nickel–Borane Unit as a Promising Strategy for Catalysis

  摘要：

  We report the synthesis and characterization of a series of nickel complexes of the chelating diphosphine-borane ligands ArB(o-Ph2PC6H4)(2) ([(DPBPh)-D-Ar]; Ar = Ph, Mes). The [(DPBPh)-D-Ar] framework supports pseudo-tetrahedral nickel complexes featuring eta(2)-B,C coordination from the ligand backbone. For the B-phenyl derivative, the adduct [(DPBPh)-D-Ph]Ni(THF) has been characterized by X-ray diffraction and features a very short interaction between nickel and the eta(2)-B,C ligand. For the B-mesityl derivative, the reduced nickel complex [(DPBPh)-D-Mes]Ni is isolated as a pseudo-three-coordinate "naked" species that undergoes reversible, nearly thermoneutral oxidative addition of dihydrogen to give a borohydrido-hydride complex of nickel(II) which has been characterized in solution by multinuclear NMR Furthermore, [(DPBPh)-D-Mes]Ni is an efficient catalyst for the hydrogenation of olefin substrates under mild conditions.

  DOI：

  10.1021/ja211419t
• 作为产物：
  描述：

  dichloro(mesityl)borane 、 (2-溴苯基)二苯基膦 在 正丁基锂 作用下， 以 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 0.5h， 以77%的产率得到MesB(o-PPh2C6H4)2
  参考文献：
  名称：

  Reversible H₂ Addition across a Nickel–Borane Unit as a Promising Strategy for Catalysis

  摘要：

  We report the synthesis and characterization of a series of nickel complexes of the chelating diphosphine-borane ligands ArB(o-Ph2PC6H4)(2) ([(DPBPh)-D-Ar]; Ar = Ph, Mes). The [(DPBPh)-D-Ar] framework supports pseudo-tetrahedral nickel complexes featuring eta(2)-B,C coordination from the ligand backbone. For the B-phenyl derivative, the adduct [(DPBPh)-D-Ph]Ni(THF) has been characterized by X-ray diffraction and features a very short interaction between nickel and the eta(2)-B,C ligand. For the B-mesityl derivative, the reduced nickel complex [(DPBPh)-D-Mes]Ni is isolated as a pseudo-three-coordinate "naked" species that undergoes reversible, nearly thermoneutral oxidative addition of dihydrogen to give a borohydrido-hydride complex of nickel(II) which has been characterized in solution by multinuclear NMR Furthermore, [(DPBPh)-D-Mes]Ni is an efficient catalyst for the hydrogenation of olefin substrates under mild conditions.

  DOI：

  10.1021/ja211419t

文献信息

• Synthesis and Reactivity of Palladium Complexes Featuring a Diphosphinoborane Ligand
  作者：Tobias Schindler、Marcel Lux、Marius Peters、Lennart T. Scharf、Hassan Osseili、Laurent Maron、Michael E. Tauchert

  DOI：10.1021/acs.organomet.5b00217

  日期：2015.5.26

  Synthetic access to the zerovalent palladium complexes [(o-Ph2PC6H4)2BPh]Pd(L)} (L = pyridine (8a), 2,6-lutidine (8b)) is reported. Structural characterization and DFT analysis of 8a revealed a strong Pd→B interaction, which appears to inhibit oxidative addition reactions. Activation of allyl acetate is possible by reversible transfer of the acetate leaving group to the ligand’s borane functionality

  据报道合成了零价钯络合物[（o -Ph 2 PC 6 H 4）2 BPh] Pd（L）}（L =吡啶（8a），2，6-二甲基吡啶（8b））。8a的结构表征和DFT分析表明，Pd→B相互作用很强，似乎抑制了氧化加成反应。乙酸烯丙酯的活化可以通过乙酸酯离去基团可逆转移至配体的硼烷官能团来实现。乙酸烯丙酯被HNEt 2烯丙基取代时的催化活性对游离乙酸酯的存在很敏感，游离乙酸酯通过可逆的硼酸盐形成降低了硼烷抑制作用。
• Reversible H₂ Addition across a Nickel–Borane Unit as a Promising Strategy for Catalysis
  作者：W. Hill Harman、Jonas C. Peters

  DOI：10.1021/ja211419t

  日期：2012.3.21

  We report the synthesis and characterization of a series of nickel complexes of the chelating diphosphine-borane ligands ArB(o-Ph2PC6H4)(2) ([(DPBPh)-D-Ar]; Ar = Ph, Mes). The [(DPBPh)-D-Ar] framework supports pseudo-tetrahedral nickel complexes featuring eta(2)-B,C coordination from the ligand backbone. For the B-phenyl derivative, the adduct [(DPBPh)-D-Ph]Ni(THF) has been characterized by X-ray diffraction and features a very short interaction between nickel and the eta(2)-B,C ligand. For the B-mesityl derivative, the reduced nickel complex [(DPBPh)-D-Mes]Ni is isolated as a pseudo-three-coordinate "naked" species that undergoes reversible, nearly thermoneutral oxidative addition of dihydrogen to give a borohydrido-hydride complex of nickel(II) which has been characterized in solution by multinuclear NMR Furthermore, [(DPBPh)-D-Mes]Ni is an efficient catalyst for the hydrogenation of olefin substrates under mild conditions.