bis(2-diphenylphosphino)(phenyl)borane | 1003001-75-9

• 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: bis(2-diphenylphosphino)(phenyl)borane
• 英文别名: PhB(C6H4PPh2)2；((Phenylboranediyl)bis(2,1-phenylene))bis(diphenylphosphane)；[2-[(2-diphenylphosphanylphenyl)-phenylboranyl]phenyl]-diphenylphosphane
• CAS: 1003001-75-9
• 化学式: C₄₂H₃₃BP₂
• 分子量: 610.483
• InChiKey: BZOFYLMIEUVWIN-UHFFFAOYSA-N

物化性质

• 沸点：
  685.0±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.72
• 重原子数：
  45
• 可旋转键数：
  9
• 环数：
  7.0
• 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：

  bis(2-diphenylphosphino)(phenyl)borane 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 生成 [2-[(2-diphenylphosphanylphenyl)-phenylboranyl]phenyl]-diphenylphosphane;nickel;oxolane
  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：

  二氯苯酚溴酯 、 [2-(diphenylphosphino)phenyl]lithium 以 甲苯 为溶剂， 以52%的产率得到bis(2-diphenylphosphino)(phenyl)borane
  参考文献：
  名称：

  Lewis Acids and Lewis Acid-Functionalized Ligands in Rhodium-Catalyzed Methyl Acetate Carbonylation

  摘要：

  The application of Lewis acids and Lewis acid-functionalized ligands as activators for methyl acetate in the rhodium-catalyzed carbonylation of methyl acetate to acetic anhydride has been investigated. The reaction of methyl acetate with B(C6F5)(3) results in the formation of the adduct [MeOAc center dot B(C6F5)(3)]. The combination of this adduct with [Rh(OAc)-(CO)(2)](2) results in a transfer of the Lewis acid to the rhodium complex, rather than an anticipated oxidative addition reaction. In a second approach, novel Lewis acid-functionalized rhodium-(I) complexes [Rh(CO)Cl(BPP)], [Rh(CO)(2)(EPP)]SbF6, and [Rh(MeCN)(2)(BPP)]SbF6 (BPP = PhB(C6H4PPh2)(2)) have been prepared. The lack of reactivity of [Rh(CO)(2)(BPP)]SbF6 toward MeOAc has shown that the rhodium boron interaction is too strong for activation of methyl acetate, and no carbonylation activity was observed under the conditions used.

  DOI：

  10.1021/om200341t

文献信息

• Palladium–Borane Cooperation: Evidence for an Anionic Pathway and Its Application to Catalytic Hydro‐/Deutero‐dechlorination
  作者：Hajime Kameo、Jun Yamamoto、Ayaka Asada、Hiroshi Nakazawa、Hiroyuki Matsuzaka、Didier Bourissou

  DOI：10.1002/anie.201909675

  日期：2019.12.19

  Metal-Lewis acid cooperation provides new opportunities in catalysis. In this work, we report a new type of palladium-borane cooperation involving anionic Pd0 species. The air-stable DPB palladium complex 1 (DPB=diphosphine-borane) was prepared and reacted with KH to give the Pd0 borohydride 2, the first monomeric anionic Pd0 species to be structurally characterized. The boron moiety acts as an acceptor

  路易斯金属酸的合作为催化提供了新的机会。在这项工作中，我们报告了一种涉及阴离子Pd0物种的新型钯-硼烷配合。制备了空气稳定的DPB钯络合物1（DPB =二膦-硼烷），并与KH反应，得到Pd0硼氢化物2，这是结构上要表征的第一个单体阴离子型Pd0。硼部分通过Pd→B相互作用在1中充当Pd的受体，但由于BH-Pd桥接，在2中充当供体。如各种（杂）芳基氯化物的加氢/氘代脱卤化反应所证实的那样，这使得C-Cl键的活化成为可能，并且该体系易于催化（20个实例，平均收率85％）。
• 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。
• Experimental and Theoretical Investigation of an S_N2-type Pathway for Borate–Fluorine Bond Cleavage by Electron-Rich Late-Transition Metal Complexes
  作者：Hajime Kameo、Yuki Baba、Shigeyoshi Sakaki、Yudai Tanaka、Hiroyuki Matsuzaka

  DOI：10.1021/acs.inorgchem.9b03053

  日期：2020.4.6

  iridium(I) and palladium(0) complexes. The selectivity of B-F σ-bond cleavage by iridium complexes was improved through the high nucleophilicity of the iridium center, implying that a different pathway from that of well-accepted F- abstraction was in effect. The palladium(0) complex was found to promote exclusive B-F σ-bond cleavage even at ambient temperature. Density functional theory (DFT) calculations

  通过与富电子的铱（I）和钯（0）配合物的反应，已通过实验实现了氟硼酸盐的BFσ键活化。通过铱中心的高度亲核性，提高了铱配合物裂解BFσ键的选择性，这表明与有效的F抽象途径不同。发现钯（0）配合物甚至在环境温度下也能促进独家的BFσ键裂解。密度泛函理论（DFT）计算表明，BFσ-键活化是通过SN2型途径发生的，据我们所知，这是过渡金属络合物介导的SN2型硼酸-氟σ键断裂的第一个提议。SN2型途径的高可行性似乎归因于过渡态的较低变形能。
• Copper(I) Complexes derived from Mono- and Diphosphino-Boranes: Cu→B Interactions Supported by Arene Coordination
  作者：M. Sircoglou、S. Bontemps、M. Mercy、K. Miqueu、S. Ladeira、N. Saffon、L. Maron、G. Bouhadir、D. Bourissou

  DOI：10.1021/ic901896z

  日期：2010.5.3

  corresponding complexes [o-iPr2P(C6H4)BPh2]Cu(μ-Cl)}22, [o-iPr2P(C6H4)BCy2]Cu(μ-Cl)}24, [o-Ph2P(C6H4)]2BPh}CuCl 7, and [o-iPr2P(C6H4)]2BPh}CuCl 8. The presence of Cu→B interactions supported by arene coordination within complexes 2, 7, and 8 has been unambiguously evidenced by NMR spectroscopy and X-ray diffraction studies. The unique η2-BC coordination mode adopted by complexes 7 and 8 has been

  单膦硼烷o - i Pr 2 P（C 6 H 4）BR 2（1：R = Ph和3：R = Cy）和二膦硼烷[ o -R 2 P（C 6 H 4）] 2 BPh （5：R = Ph和6：R = i Pr）易于与CuCl反应，得到相应的络合物[ o - i Pr 2 P（C 6 H 4）BPh 2 ] Cu（μ-Cl）} 2 2， [ø -我镨2 P（C 6 H ^ 4）BCY 2 ]的Cu（μ-Cl）的} 2 4，[ ö -Ph 2 P（C 6 H ^ 4）] 2 BPH}的CuCl 7，和[ ø - i Pr 2 P（C 6 H 4）] 2 BPh} CuCl 8。铜→乙相互作用的复合物中由芳烃协调支持存在2，7，和8NMR光谱学和X射线衍射研究已清楚地证明了这一点。独特η 2由络合物通过-BC协调模式7和8已经通过密度泛函理论（DFT）计算被彻底分析。
• Square‐Planar Anionic Pt ⁰ Complexes
  作者：Hajime Kameo、Yudai Tanaka、Yoshihiro Shimoyama、Daisuke Izumi、Hiroyuki Matsuzaka、Yumiko Nakajima、Pierre Lavedan、Arnaud Le Gac、Didier Bourissou

  DOI：10.1002/anie.202301509

  日期：——

  The use of a diphosphine-borane ligand DPB enables straightforward access to anionic Pt0 complexes. [(DPB)PtX]− complexes were isolated and fully characterized. They represent unique examples of square-planar Pt0 complexes, as substantiated by X-ray diffraction analyses, X-ray photoelectron spectroscopy and DFT calculations.

  使用二膦-硼烷配体 DPB 可以直接获得阴离子 Pt 0配合物。[(DPB)PtX] −分离并充分表征了复合物。它们代表了方形平面 Pt 0配合物的独特例子，如 X 射线衍射分析、X 射线光电子能谱和 DFT 计算所证实的那样。