PhB(o-iPr₂PC₆H₄)₂ | 885516-55-2

• 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: PhB(o-iPr₂PC₆H₄)₂
• 英文别名: ^PhDPB^iPr；[o-(iPr2P)C6H4]2BPh；[2-[[2-Di(propan-2-yl)phosphanylphenyl]-phenylboranyl]phenyl]-di(propan-2-yl)phosphane
• CAS: 885516-55-2
• 化学式: C₃₀H₄₁BP₂
• 分子量: 474.414
• InChiKey: GBDGTASGPBHTED-UHFFFAOYSA-N

物化性质

• 熔点：
  95-97 °C
• 沸点：
  556.4±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.05
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  PhB(o-iPr₂PC₆H₄)₂ 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 反应 21.0h， 生成 [^PhDPB^iPr]Ni(N₂)
  参考文献：
  名称：

  的D10的Ni-（H2）加合物作为中间体H中？^ h氧化加成跨越倪？债券

  摘要：

  双官能EH活化为设计具有后第一排金属（例如Ni）的双电子还原催化剂提供了一种有前途的方法。为此，我们一直在晚期金属硼烷中进行H 2活化反应，在此描述了一种由二膦-硼烷负载的Ni-（H 2）络合物[（Ph DPB i Pr）Ni（H 2）]，其中在解决方案中具有特征。1 H NMR光谱证实了完整的H 2配体的存在。一系列数据，包括电子结构计算的，表明广告10配置为[（博士DPB我镨）Ni（H 2）]最合适。这种结构在过渡金属H 2加合物中极为罕见。非经典ħ 2加合物是在H完全活化的中间体2横跨在Ni 乙相互作用。反应坐标分析表明，硼氢化烷镍亚基的Ni和B中心都可以协同激活H 2配体，从而突出了硼烷配体在稳定d 10 Ni-（H 2）相互作用以及稳定d 10 Ni-（H 2）相互作用中的重要作用。H-H裂解步骤。

  DOI：

  10.1002/anie.201308175
• 作为产物：
  描述：

  二氯苯酚溴酯 、 (2-bromophenyl)diisopropylphosphine 在 n-C₄H₉Li 作用下， 以 not given 为溶剂， 以70%的产率得到PhB(o-iPr₂PC₆H₄)₂
  参考文献：
  名称：

  Quasi-Thermoneutral P → B Interactions within Di- and Tri-Phosphine Boranes

  摘要：

  Spectroscopic, structural, and theoretical evidence is provided for both open (no intramolecular P -> B interaction) and closed (with intramolecular P -> B interaction) forms of the di- and tri-phosphine boranes [o-(iPr(2)P)C6H4](2)BPh (2) and [o-(iPr(2)P)C6H4](3)B (3).

  DOI：

  10.1021/ic7006556

文献信息

• Silver halide complexes of a borane/bis(phosphine) ligand
  作者：Yihan Cao、Wei-Chun Shih、Nattamai Bhuvanesh、Oleg V. Ozerov

  DOI：10.1039/c9dt02100k

  日期：——

  Silver halide complexes of a borane/bis(phosphine) ligand have been prepared and characterized. With AgF, the borane abstracts fluoride, resulting in a zwitterionic complex. With AgCl, AgBr, and AgI, the halide stays coordinated to Ag, with little to no Ag–B interaction.

  已经制备并表征了硼烷/双（膦）配体的卤化银配合物。用AgF，硼烷提取氟化物，生成两性离子络合物。使用AgCl，AgBr和AgI，卤化物与Ag保持配位，几乎没有Ag-B相互作用。
• 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。
• Olefin hydroboration catalyzed by an iron-borane complex
  作者：Laura A. Grose、Darren Willcox

  DOI：10.1039/d3cc00494e

  日期：——

  The well-defined iron(0) complex [(iPrDPBPh)Fe2-(μ-1,2-N2)] (A) reacts with HBpin to afford the complex [(η3-H2iPrDPB)Fe(η3-H2Bpin)] (B) via oxidative addition of the H–B bond. Complex A is an effective pre-catalyst for the hydroboration of a range of olefins in synthetically useful yields (typically >80%) under neat conditions.

  定义明确的铁 (0) 络合物 [( i Pr DPB Ph )Fe 2 -(μ-1,2-N 2 )] (A) 与 HBpin 反应生成络合物 [( η 3 -H 2 i Pr DPB )Fe( η 3 -H 2 Bpin)] (B)通过H–B 键的氧化加成。络合物 A 是一种有效的预催化剂，可在纯净条件下以合成有用的产率（通常 >80%）对一系列烯烃进行硼氢化。
• E–H Bond Activations and Hydrosilylation Catalysis with Iron and Cobalt Metalloboranes
  作者：Mark A. Nesbit、Daniel L. M. Suess、Jonas C. Peters

  DOI：10.1021/acs.organomet.5b00530

  日期：2015.10.12

  An exciting challenge in transition metal catalyst design is to explore whether earth-abundant base metals such as Fe, Co, and Ni can mediate two-electron reductive transformations that their precious metal counterparts (e.g., Ru, Rh, Ir, and Pd) are better known to catalyze. Organometallic metalloboranes are an interesting design concept in this regard because they can serve as organometallic frustrated Lewis pairs. To build on prior studies with nickel metalloboranes featuring the DPB and (DPBMes)-D-Ph ligands in the context of H-2 and slime activation and catalysis (DPB = bis(o-diisopropylphosphinophenyl)phenylborane, (DPBMes)-D-Ph = bis (o-diphenylphosphinophenyl)mesitylborane), we now explore the reactivity of iron, [(DPB)Fe](2)(N-2), 1, and cobalt, (DPB)Co(N-2), 2, metalloboranes toward a series of substrates with E-H bonds (E = O, S, C, N) including phenol, thiophenol, benzo[h]quinoline, and 8-aminoquinoline. In addition to displaying high stoichiometric E-H bond activation reactivity, complexes 1 and 2 prove to be more active catalysts for the hydrosilylation of ketones and aldehydes with diphenylsilane relative to ((DPBMes)-D-Ph)Ni. Indeed, 2 appears to be the most active homogeneous cobalt catalyst reported to date for the hydrosilylation of acetophenone under the conditions studied.
• Facile Insertion of Rh and Ir into a Boron–Phenyl Bond, Leading to Boryl/Bis(phosphine) PBP Pincer Complexes
  作者：Wei-Chun Shih、Weixing Gu、Morgan C. MacInnis、Samuel D. Timpa、Nattamai Bhuvanesh、Jia Zhou、Oleg V. Ozerov

  DOI：10.1021/jacs.5b11706

  日期：2016.2.24

  The unexpectedly facile insertion of Rh or Ir into a B-Ph bond (reversible for Rh) converts a borane/bis(phosphine) precursor into a boryl/bis-(phosphine) PBP pincer ligand. Interconversions between the boryl/borane/borate central functionality are demonstrated in reactions with dihydrogen.