tris-(o-diisopropylphophinophenyl)borane | 944384-95-6

• 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: tris-(o-diisopropylphophinophenyl)borane
• 英文别名: tris[2-(diisopropylphosphino)phenyl]borane；tris(o-diisopropylphosphinophenyl)borane；TPB；tris(phosphino)borane；[o-(iPr2P)C6H4]3B；[2-Bis[2-di(propan-2-yl)phosphanylphenyl]boranylphenyl]-di(propan-2-yl)phosphane；[2-bis[2-di(propan-2-yl)phosphanylphenyl]boranylphenyl]-di(propan-2-yl)phosphane
• CAS: 944384-95-6
• 化学式: C₃₆H₅₄BP₃
• 分子量: 590.557
• InChiKey: HAPFABUKKFCRAP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.97
• 重原子数：
  40
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  tris-(o-diisopropylphophinophenyl)borane 以 苯 为溶剂， 生成 (三(膦)硼烷)Fe(N2)
  参考文献：
  名称：

  三足 P3XFe–N2 配合物（X = B、Al、Ga）：顶端原子对键合、电子结构和催化 N2 转化为 NH3 的影响

  摘要：

  由三齿、四齿 P 3 X配体（X = B、C、Si）连接的铁末端二氮配合物先前已被证明可以介导与外部质子和电子源的催化 N 2 -至 -NH 3转化（N 2 RR）。在这组化合物中，三(膦基)硼烷 (P 3 B ) 系统在迄今为止探讨的所有条件下都是最活跃的。为了进一步探讨顶端路易斯酸性原子对结构、键合和 N 2 RR 活性的影响，由类似的第 13 族三（膦基）丙烷（P 3 Al ）和三（膦基）镓烷（P 3 Ga ) 配体被合成。 P 3 X Fe–N 2 [0/1−]化合物（X = B、Al、Ga）系列具有相似的电子结构、N 2活化程度和几何灵活性（根据光谱、结构、电化学和化学性质确定）计算（DFT）研究。然而，用 HBAr F 4 /KC 8形式的过量酸/还原剂处理 [Na(12-crown-4) 2 ][P 3 X Fe–N 2 ] (X = Al, Ga) 仅产生 2.5 ±每Fe分别为0

  DOI：

  10.1021/acs.inorgchem.0c03354
• 作为产物：
  描述：

  [o-(iPr2P)C6H4]3B 以 四氢呋喃 为溶剂， 生成 tris-(o-diisopropylphophinophenyl)borane
  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

• Terminal Iron Dinitrogen and Iron Imide Complexes Supported by a Tris(phosphino)borane Ligand
  作者：Marc-Etienne Moret、Jonas C. Peters

  DOI：10.1002/anie.201006918

  日期：2011.2.25

  Adaptable metallaboratranes: A tris‐ (phosphino)borane ligand stabilizes both low‐valent FeN2 complexes and a mid‐valent imido species with a FeNAr bond, thanks to its ability to shuttle between trigonal‐bipyramidal and pseudotetrahedral geometries by elongation of the apical iron–boron bond (see picture).

  适应性强的金属硼烷：三（膦基）硼烷配体稳定低价 Fe  N 2配合物和具有 FeNAr 键的中价亚胺物种，这要归功于其通过伸长在三角双锥和假四面体几何结构之间穿梭的能力顶端铁硼键（见图）。
• A Polar Copper–Boron One-Electron σ-Bond
  作者：Marc-Etienne Moret、Limei Zhang、Jonas C. Peters

  DOI：10.1021/ja4006578

  日期：2013.3.13

  and Li2(+) and in highly unstable species generated in solid matrices. Only in the past decade was bona fide one-electron bonding observed for molecules in fluid solution. Here we report the isolation and structural characterization of a thermally stable compound featuring a Cu-B one-electron bond, as well as its oxidized (nonbonded) and reduced (two-electrons-bonded) congeners. This triad provides

  几乎所有的化学键都由两个原子共享的一对或几对电子组成。由在两个相邻原子上离域的单个电子组成的 σ 键的例子直到最近才在气相阳离子中发现，例如 H2(+) 和 Li2(+) 以及在固体基质中产生的高度不稳定的物质。仅在过去十年中才观察到流体溶液中分子的真正单电子键合。在这里，我们报告了具有 Cu-B 单电子键的热稳定化合物的隔离和结构表征，以及其氧化（非键合）和还原（双电子键合）同系物。这种三元组提供了一个极好的机会来研究作为电子计数函数的金属硼烷中 σ 键合的程度。
• Characterization of a Proposed Terminal Iron(III) Nitride Intermediate of Nitrogen Fixation Stabilized by a Trisphosphine‐Borane Ligand
  作者：Dirk J. Schild、Lucie Nurdin、Marc‐Etienne Moret、Paul H. Oyala、Jonas C. Peters

  DOI：10.1002/anie.202209655

  日期：2022.10.24

  The generation and low-temperature characterization of a terminally bound iron(III) nitride, P3BFe(N) (P3B=tris(o-diisopropylphosphinophenyl)borane), a plausible intermediate of iron-mediated nitrogen fixation, is reported. EPR spectroscopy supported by DFT calculations define a 2A ground state electronic structure for this C3-symmetric nitride, placing an unpaired spin in a sigma orbital along the

  报道了末端结合的氮化铁（III）P 3 BFe(N)（P 3 B=三（邻二异丙基膦苯基）硼烷）的生成和低温表征，它是铁介导的固氮的可能中间体。DFT 计算支持的 EPR 光谱定义了这种C 3对称氮化物的2 A 基态电子结构，将不成对的自旋放置在沿着 B−Fe−N 矢量的 sigma 轨道中。
• Dihydrogen Binding to Isostructural <i>S</i> = ¹/₂ and <i>S</i> = 0 Cobalt Complexes
  作者：Daniel L. M. Suess、Charlene Tsay、Jonas C. Peters

  DOI：10.1021/ja305248f

  日期：2012.8.29

  Two isostructural, nonclassical Co(H(2)) complexes are prepared from their Co(N(2)) precursors using tris(phosphino)silyl and tris(phosphino)borane ancillary ligands. Comproportionation of CoBr(2) and Co metal in the presence of TPB (tris-(o-diisopropylphophinophenyl)borane) gives (TPB)CoBr (4). One-electron reduction of 4 triggers N(2) binding to give (TPB)Co(N(2)) (2-N(2)) which is isostructural to previously reported [SiP(3)]Co(N(2)) (1-N(2)) ([SiP(3)] = tris-(o-diisopropylphosphinophenyl)silyl). Both 1-N(2) and 2-N(2) react with 1 atm H(2) to generate thermally stable H(2) complexes 1-H(2) and 2-H(2), respectively. Both complexes are characterized by a suite of spectroscopic techniques in solution and by X-ray crystallography. The H(2) and N(2) ligands in 2-H(2) and 2-N(2) are labile under ambient conditions and the binding equilibria are observable by temperature-dependent UV/vis. A van't Hoff analysis allows for the ligand binding energetics to be determined (H(2): ΔH(o) = -12.5(3) kcal mol(-1) and ΔS(o) = -26(3) cal K(-1) mol(-1); N(2): ΔH(o) = -13.9(7) kcal mol(-1) and ΔS(o) = -32(5) cal K(-1) mol(-1)).
• Hydricity of an Fe–H Species and Catalytic CO₂ Hydrogenation
  作者：Henry Fong、Jonas C. Peters

  DOI：10.1021/ic502508p

  日期：2015.6.1

  Despite renewed interest in carbon dioxide (CO2) reduction chemistry, examples of homogeneous iron catalysts that hydrogenate CO2 are limited compared to their noble-metal counterparts. Knowledge of the thermodynamic properties of iron hydride complexes, including M-H hydricities (Delta GH(-)), could aid in the development of new iron-based catalysts. Here we present the experimentally determined hydricity of an iron hydride complex: (SiP(iPr)(3))Fe(H-2)(H), Delta GH(-)) = 54.3 +/- 0.9 kcal/mol [SiP(iPr)(3) = [Si(o-C(6)H(4)PiPr(2))(3)](-)]. We also explore the CO2 hydrogenation chemistry of a series of triphosphinoiron complexes, each with a distinct apical unit on the ligand chelate (Si-, C-, PhB-, N, B). The silyliron (SiP(R)(3))Fe (R = iPr and Ph) and boratoiron (PhBP3iPr)Fe (PhBP3ipr = [PhB(CH(2)PiPr(2))(3)](-)) systems, as well as the recently reported (CP3iPr)Fe (CP3iPr = [C(o-C(6)H(4)PiPr(2))(3)](-)), are also catalysts for CO2 hydrogenation in methanol and in the presence of triethylamine, generating methylformate and triethylammonium formate at up to 200 TON using (SiP3Ph)FeCl as the precatalyst. Under stoichiometric conditions, the iron hydride complexes of this series react with CO2 to give formate complexes. Finally, the proposed mechanism of the (SiP3iPr)-Fe system proceeds through a monohydride intermediate (SiP3iPr)Fe(H-2)(H), in contrast to that of the known and highly active tetraphosphinoiron, (tetraphos)Fe (tetraphos = P(o-C6H4PPh2)(3)), CO2 hydrogenation catalyst.