1,5-di(Ph)-3,7-di(Cy)-1,5-diaza-3,7-diphosphacyclooctane | 75593-75-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,5-di(Ph)-3,7-di(Cy)-1,5-diaza-3,7-diphosphacyclooctane
• 英文别名: 1,5-diphenyl-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane；3,7-Dicyclohexyl-1,5-diphenyl-1,5,3,7-diazadiphosphocane
• CAS: 75593-75-8
• 化学式: C₂₈H₄₀N₂P₂
• 分子量: 466.587
• InChiKey: PTNIEWBVQNVUDU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 1,5-di(Ph)-3,7-di(Cy)-1,5-diaza-3,7-diphosphacyclooctane 以 四氢呋喃 、 甲苯 为溶剂， 生成 [Ni(1,5-di(Ph)-3,7-di(Cy)-1,5-diaza-3,7-diphosphacyclooctane)2]
  参考文献：
  名称：

  构象动力学和质子接力定位在镍基催化剂用于制氢和氧化

  摘要：

  的[镍（P - [R 2 Ñ - [R ' 2）2 ] 2+的复合物（其中，P [R 2 Ñ - [R ' 2是1,5--R'-3,7--R-1,5-二氮杂-3,7-二磷环辛烷）是用于H 2产生和氧化的快速电催化剂。第五种配体（CH 3 CN或BF 4 –）的结合或椅子/船的异构化有可能通过阻止H 2的添加而减慢催化作用。或由不正确地定位所述侧基胺。我们报告了一系列镍配合物，其特征在于用NMR光谱和理论模型来检查第五配体对镍（II）配合物，其中包括CH的效果的结构动力学3 CN，BF 4 - ，氯-和H - ，以及在镍（II）和Ni（0）氧化态之间动力学的差别。观察到的快速交换处理[镍（CH 3 CN）（P - [R 2 Ñ - [R ' 2）2 ] 2+的复合物，与速率为10 4到10个7小号-1根据在P中的磷和氮的取代基- [R 2 Ñ - [R ' 2配体。已确定这种交换过程是通过多

  DOI：

  10.1021/om400695w
• 作为产物：
  描述：

  环已基膦 以 乙醇 为溶剂， 反应 12.0h， 生成 1,5-di(Ph)-3,7-di(Cy)-1,5-diaza-3,7-diphosphacyclooctane
  参考文献：
  名称：

  Coordination and conformational isomers in mononuclear iron complexes with pertinence to the [FeFe] hydrogenase active site

  摘要：

  制备了类型为[Fe(X-bdt)(P^R_2N^Ph_2)(CO)]的6种Fe配合物，并展示了通过配体修饰调节它们的电子性质的可能性。红外光谱和计算研究表明，这些化合物在溶液中存在多种异构体的混合物。

  DOI：

  10.1039/c3dt53268b
• 作为试剂：
  描述：

  2,6-二甲基溴苯 、 苯硼酸 在 palladium diacetate 、 potassium carbonate 、 1,5-di(Ph)-3,7-di(Cy)-1,5-diaza-3,7-diphosphacyclooctane 作用下， 以 水 为溶剂， 反应 2.0h， 以83%的产率得到1,3-二甲基-2-苯基苯
  参考文献：
  名称：

  低催化剂用量的铃木-宫浦交叉偶联偶联反应：纯净水中的绿色可持续方案

  摘要：

  Suzuki-Miyaura偶联反应代表了20世纪最重要的合成转化之一。但是，使用有毒有机溶剂仍然是一项科学挑战，也是经济和生态相关性以及良性的一个方面。水作为一种反应介质，人们发现它非常有效地克服了其中一些问题。在本手稿中，我们以纯净的方式描述了Suzuki-Miyaura偶联反应水，不使用任何相转移试剂。值得注意的是，该协议还适用于具有高周转率的超低负载催化剂，并且还能够偶联具有挑战性的底物，如芳基氯化物。

  DOI：

  10.1039/c0dt01637c

文献信息

• Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid
  作者：Souvik Roy、Bhaskar Sharma、Jacques Pécaut、Philippe Simon、Marc Fontecave、Phong D. Tran、Etienne Derat、Vincent Artero

  DOI：10.1021/jacs.6b11474

  日期：2017.3.15

  dimethylformamide (DMF)/water mixtures (Faradaic efficiency of 90 ± 10%) at moderate overpotentials (500-700 mV in DMF measured at the middle of the catalytic wave). The [CpCo(PR2NR'2)I]+ compounds contain diphosphine ligands, PR2NR'2, with two pendant amine residues that act as proton relays during CO2-reduction catalysis and tune their activity. Four different PR2NR'2 ligands with cyclohexyl or phenyl

  我们在此报告了一系列基于地球丰富元素的新型 CO2 还原分子催化剂，这些催化剂对于在中等过电位下在二甲基甲酰胺 (DMF)/水混合物（法拉第效率为 90 ± 10%）中生产甲酸非常有选择性（ 500-700 mV 在 DMF 中在催化波的中间测量）。[CpCo(PR2NR'2)I]+ 化合物包含二膦配体 PR2NR'2，带有两个侧链胺残基，在 还原催化过程中充当质子中继并调整其活性。使用了四种不同的PR2NR'2配体，磷上有环己基或苯基取代基，氮上有苄基或苯基取代基，具有给电子膦配体最多和胺功能最基本的化合物在系列中表现最好，周转频率> 1000 秒-1。最先进的催化性能基准将这种新型钴基配合物列为迄今为止开发的最有前途的 -甲酸还原催化剂；解决稳定性问题将有助于进一步改进。机理研究和密度泛函理论模拟证实了胺基团在氢化物从 Co 中心转移到 分子期间通过与水分子形成氢键来稳定关键中间体的作用。
• Synthesis, Structural, and Electrocatalytic Reduction Studies of [Pd(P₂N₂)₂]²⁺ Complexes
  作者：Candace S. Seu、David Ung、Michael D. Doud、Curtis E. Moore、Arnold L. Rheingold、Clifford P. Kubiak

  DOI：10.1021/om400472s

  日期：2013.8.26

  A series of four new bis-P2N2 (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane) Pd(II) complexes were synthesized and characterized by spectroscopy, electrochemistry, and X-ray crystallography. The compounds crystallize in square planar or tetrahedrally distorted geometries and exhibit a single quasi-reversible 2e(-) Pd(II/0) redox couple in voltammetric studies. [Pd((P2N2Bn)-N-Ph)(2)](2+) and [Pd((P2N2Ph)-N-Me)(2)](2+) were tested for electrochemical CO2 reduction in the presence of excess protons and found to preferentially produce H-2.
• Incorporation of Pendant Bases into Rh(diphosphine)₂ Complexes: Synthesis, Thermodynamic Studies, And Catalytic CO₂ Hydrogenation Activity of [Rh(P₂N₂)₂]⁺ Complexes
  作者：Alyssia M. Lilio、Mark H. Reineke、Curtis E. Moore、Arnold L. Rheingold、Michael K. Takase、Clifford P. Kubiak

  DOI：10.1021/jacs.5b04291

  日期：2015.7.1

  A series of five [Rh(P2N2)2](+) complexes (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane) have been synthesized and characterized: [Rh(P(Ph)2N(Ph)2)2](+) (1), [Rh(P(Ph)2N(Bn)2)2](+) (2), [Rh(P(Ph)2N(PhOMe)2)2](+) (3), [Rh(P(Cy)2N(Ph)2)2](+) (4), and [Rh(P(Cy)2N(PhOMe)2)2](+) (5). Complexes 1-5 have been structurally characterized as square planar rhodium bis-diphosphine complexes with slight tetrahedral distortions. The corresponding hydride complexes 6-10 have also been synthesized and characterized, and X-ray diffraction studies of HRh(P(Ph)2N(Bn)2)2 (7), HRh(P(Ph)2N(PhOMe)2)2 (8) and HRh(P(Cy)2N(Ph)2)2 (9) show that the hydrides have distorted trigonal bipyramidal geometries. Equilibration of complexes 2-5 with H2 in the presence of 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane (Verkade's base) enabled the determination of the hydricities and estimated pKa's of the Rh(I) hydride complexes using the appropriate thermodynamic cycles. Complexes 1-5 were active for CO2 hydrogenation under mild conditions, and their relative rates were compared to that of [Rh(depe)2](+), a nonpendant-amine-containing complex with a similar hydricity to the [Rh(P2N2)2](+) complexes. It was determined that the added steric bulk of the amine groups on the P2N2 ligands hinders catalysis and that [Rh(depe)2](+) was the most active catalyst for hydrogenation of CO2 to formate.
• Design and Characterization of Phosphine Iron Hydrides: Toward Hydrogen-Producing Catalysts
  作者：Katharina Weber、Thomas Weyhermüller、Eckhard Bill、Özlen F. Erdem、Wolfgang Lubitz

  DOI：10.1021/acs.inorgchem.5b00911

  日期：2015.7.20

  Diamagnetic iron chloro compounds [((P2N2Ph)-N-Ph)FeCp*Cl] [1Cl] and [((P2N2Ph)-N-Cy)FeCp*Cl] [2Cl] and the corresponding hydrido complexes [((P2N2Ph)-N-Ph)- FeCp*H] [1H] and [((P2N2Ph)-N-Cy)FeCp*H] [2H] have been synthesized and characterized by NMR spectroscopy, electrochemical studies, electronic absorption, and Fe-57 Mossbauer spectroscopy ((P2N2Ph)-N-Ph = 1,3,5,7-tetraphenyl-1,5-diphospha3,7-diazacyclooctane, (P2N2Ph)-N-Cy = 1,5-dicydohexyl-3,7-diphenyl-1,5-diphospha-3,7-diazacydooctane, Cp* = pentamethylcydopentadienyl). Molecular structures of [2Cl], [1H], and [2H], derived from single-crystal X-ray diffraction, revealed that these compounds have a typical piano-stool geometry. The results show that the electronic properties of the hydrido complexes are strongly influenced by the substituents at the phosphorus donor atoms of the (P2N2Ph)-N-R ligand, whereas those of the chloro complexes are less affected. These results illustrate that the hydride is a strong-field ligand, as compared to chloride, and thus leads to a significant degree of covalent character of the iron hydride bonds. This is important in the context of possible catalytic intermediates of iron hydrido species, as proposed for the catalytic cycle of [FeFe] hydrogenases and other synthetic catalysts. Both hydrido compounds [1H] and [2H] show enhanced catalytic currents in cyclic voltammetry upon addition of the strong add trifluoromethanesulfonimide [NHTf2] (pKaMeCN = 1.0) In contrast Bu related complex [((PNBn)-N-tBu)(2)(FeCpH)-H-C6F5], which was reported by Liu et al. (Nat. Chem. 2O13,5, 228-233) to be an electrocatalyst for hydrogen splitting, the here presented hydride complexes [1H] and [2H] show the tendency for electrocatalytic hydrogen production. Hence, the catalytic direction of this class of monoiron compounds can be reversed by specific ligand modifications.
• Electrocatalytic Oxidation of Formate by [Ni(P^R₂N^R′₂)₂(CH₃CN)]²⁺ Complexes
  作者：Brandon R. Galan、Julia Schöffel、John C. Linehan、Candace Seu、Aaron M. Appel、John A. S. Roberts、Monte L. Helm、Uriah J. Kilgore、Jenny Y. Yang、Daniel L. DuBois、Clifford P. Kubiak

  DOI：10.1021/ja204489e

  日期：2011.8.17

  [Ni((PRN2R')-N-2)(2)(CH3CN)](2+) complexes with R. = Ph, R'= 4-MeOPh or R = Cy, R' = Ph, and a mixed-ligand [Ni(p(2)(R)N(2)(R'))(p(R"):NwTR2) (rw IN (CN)-C-13)](2+) with R = Cy, R' = Ph, R" = Ph, have been synthesized and characterized by single-crystal X-ray crystallography. These and previously reported complexes are shown to be electrocatalysts for the oxidation of formate in solution to produce CO2, protons, and electrons, with rates that are first-order in catalyst and formate at formate concentrations below similar to 0.04 M (34 equiv). At concentrations above similar to 0.06 M formate (52 equiv), catalytic rates become nearly independent of formate concentration. For the catalysts studied, maximum observed turnover frequencies vary from <1.1 to 15.8 s(-1) at room temperature, which are the highest rates yet reported for formate oxidation by homogeneous catalysts. These catalysts are the only base-metal electrocatalysts as well as the only homogeneous electrocatalysts reported to date for the oxidation of formate. An acetate complex demonstrating an eta(1)-OC(O)CH3 binding mode to nickel has also been synthesized and characterized by single-crystal X-ray crystallography. Based on this structure and the electrochemical and spectroscopic data, a mechanistic scheme for electrocatalytic formate oxidation is proposed which involves formate binding followed by a rate-limiting proton and two-electron transfer step accompanied by CO2 liberation. The pendant amines have been demonstrated to be essential for electrocatalysis, as no activity toward formate oxidation was observed for the similar [Ni(depe)(2)](2+) (depe = 1,2-bis(diethylphosphino)ethane) complex.