1,5-di-(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane | 1297291-68-9

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: 1,5-di-(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane
• 英文别名: 1,5-di-(tert-butyl)-3,7-di-cyclohexyl-1,5,3,7-diazadiphosphocycloctan；((CH2)2P(Cy)N(t-Bu))2；PCy2Nt-Bu2；1,5-Ditert-butyl-3,7-dicyclohexyl-1,5,3,7-diazadiphosphocane；1,5-ditert-butyl-3,7-dicyclohexyl-1,5,3,7-diazadiphosphocane
• CAS: 1297291-68-9
• 化学式: C₂₄H₄₈N₂P₂
• 分子量: 426.606
• InChiKey: SQTAXINGISTDLT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  1,5-di-(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane 在 溴 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  通过配体-配体-协同作用微调杂配钼配合物的氧化还原性质

  摘要：

  引入配体-配体协同性作为微调分子复合物氧化还原特性的新选择。当将二硫烯和 1,5-二氮杂-3,7-二磷酸环辛烷配体结合在一个复合物中时，发现了这种效果。在电化学测量过程中，第二个配体球中的非共价相互作用导致两个配体之间的电子对话，这对观察到的氧化还原转变产生了前所未有的影响。

  DOI：

  10.1002/anie.202303151
• 作为产物：
  描述：

  Cyclohexyl-phosphonic acid diethyl ester 在 lithium aluminium tetrahydride 作用下， 以 乙醚 、 乙醇 、 水 为溶剂， 生成 1,5-di-(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane
  参考文献：
  名称：

  通过配体-配体-协同作用微调杂配钼配合物的氧化还原性质

  摘要：

  引入配体-配体协同性作为微调分子复合物氧化还原特性的新选择。当将二硫烯和 1,5-二氮杂-3,7-二磷酸环辛烷配体结合在一个复合物中时，发现了这种效果。在电化学测量过程中，第二个配体球中的非共价相互作用导致两个配体之间的电子对话，这对观察到的氧化还原转变产生了前所未有的影响。

  DOI：

  10.1002/anie.202303151

文献信息

• Hydrogen oxidation catalysis by a nickel diphosphine complex with pendant tert-butyl amines
  作者：Jenny Y. Yang、Shentan Chen、William G. Dougherty、W. Scott Kassel、R. Morris Bullock、Daniel L. DuBois、Simone Raugei、Roger Rousseau、Michel Dupuis、M. Rakowski DuBois

  DOI：10.1039/c0cc03246h

  日期：——

  A bis-diphosphine nickel complex with tert-butyl functionalized pendant amines [Ni(PCy2Nt-Bu2)2]2+ has been synthesized. It is a highly active electrocatalyst for the oxidation of hydrogen in the presence of base. The turnover rate of 50 s−1 under 1.0 atm H2 at a potential of −0.77 V vs. the ferrocene couple is 5 times faster than the rate reported heretofore for any other synthetic molecular H2 oxidation catalyst.

  我们合成了一种具有叔丁基官能化悬垂胺的双二膦镍配合物 [Ni(PCy2Nt-Bu2)2]2+。它是一种高活性的电催化剂，可在碱存在下氧化氢气。在 1.0 atm 的 H2 条件下，与二茂铁对偶的电位为 -0.77 V，其转化率为 50 s-1，比迄今为止报道的任何其他合成分子 H2 氧化催化剂的转化率快 5 倍。
• Two Pathways for Electrocatalytic Oxidation of Hydrogen by a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second Coordination Sphere
  作者：Jenny Y. Yang、Stuart E. Smith、Tianbiao Liu、William G. Dougherty、Wesley A. Hoffert、W. Scott Kassel、M. Rakowski DuBois、Daniel L. DuBois、R. Morris Bullock

  DOI：10.1021/ja400705a

  日期：2013.7.3

  acetonitrile for the oxidation of H2 depends on base size, with larger bases (NEt3, t-BuNH2) resulting in much slower catalysis than n-BuNH2. The addition of water accelerates the rate of catalysis by facilitating deprotonation of the hydrogen addition product before oxidation, especially for the larger bases NEt3 and t-BuNH2. This catalytic pathway, where deprotonation occurs prior to oxidation, leads to an

  在第二配位球中含有侧链胺的镍双（二膦）络合物 [Ni(P(Cy)2N(t-Bu)2)2](BF4)2 (P(Cy)2N(t-Bu)2 = 1,5-二（叔丁基）-3,7-二环己基-1,5-二氮杂-3,7-二磷酸环辛烷）是一种用于氢氧化的电催化剂。向 Ni(II) 络合物中加入氢得到双质子化 Ni(0) 络合物 [Ni(P(Cy)2N(t-Bu)2H)2]( )2 的三种异构体。使用热化学循环中的 pKa 值和 Ni(II/I) 和 Ni(I/0) 氧化还原电位，氢加成到 [Ni(P(Cy)2N(t-Bu)2)2]( 2+) 被确定为 -7.9 kcal mol(-1)。在干燥乙腈中观察到的 H2 氧化催化速率取决于碱大小，较大的碱（NEt3、t-BuNH2）导致比 n-BuNH2 慢得多的催化。水的加入通过促进氧化前氢加成产物的去质子化来加速催化速率，尤其是对于较大的碱 NEt3 和 t
• Dynamics and Coordination of a P2N2 Ligand – from Twisted Conformation to Chelation
  作者：Benedict J. Elvers、Christian Fischer、Carola Schulzke

  DOI：10.1002/chem.202304103

  日期：2024.4.25

  Based on their general spacial flexibility, their Lewis and Brønsted basicity, and ability to mimic second sphere effects the 1,5‐diaza‐3,7‐diphosphacyclooctane ligand family and their complexes have regained substantial scientific interest. It was now possible to structurally analyze a recently reported member of this family with p‐tolyl and t‐butyl substituents on P and N, respectively, (P2p‐tolN2tBu). Notably, the ligand crystallizes with a ‘twisted’ backbone. This compound is the very first of its kind to have been unambiguously characterized with regard to its chemical and molecular structure as being in this conformation. A temperature‐dependent NMR study provides insight into the molecular dynamics of two isomers in solution, which are most likely also both twisted, as judged by the observed limited reactivity. Despite the in principle unfavorable conformation of the free ligand, it was successfully chelated to tungsten and molybdenum centers in mononuclear carbonyl complexes. The ligand, a derivative thereof and four new complexes were comprehensively characterized and analyzed in comparison. This includes single crystal XRD molecular structures of P2p‐tolN2tBu and all four complexes. P2p‐tolN2tBu, regardless of its twisted conformation, is able to coordinate to metal centers given that enough energy (heat) for a conformational change is provided.