1,5-diphenyl-3,7-dibenzyl-1,5-diaza-3,7-diphosphacyclooctane | 1340586-41-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,5-diphenyl-3,7-dibenzyl-1,5-diaza-3,7-diphosphacyclooctane
• CAS: 1340586-41-5
• 化学式: C₃₀H₃₂N₂P₂
• 分子量: 482.545
• InChiKey: XVZPXLLBSRACQJ-AQOUDTPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.21
• 重原子数：
  34.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  6.48
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,5-diphenyl-3,7-dibenzyl-1,5-diaza-3,7-diphosphacyclooctane 、 nickel dichloride 以 乙腈 为溶剂， 生成 C₃₀H₃₂N₂NiP₂⁽²⁺⁾*2Cl^(1-)
  参考文献：
  名称：

  镍与含有 P 和 N 原子作为配位位点的环状配体的配合物：用于氢氧化的新型仿生催化剂

  摘要：

  镍与含有磷和氮原子作为配位位点的新型环状配体的配合物是新型有效的氢氧化催化剂。对其电化学性质的系统研究使得可以根据还原中电子转移过程的顺序 (MII-MI-M0) 以及溶剂和反离子的性质将所讨论的镍系统分为四组。建立了涉及镍配合物与 P,N 环配体在催化剂配位球中的 H2 氧化反应中的催化转化规律以及配合物结构与其氧化还原性能之间的相关性。最有效的催化剂在磷原子上含有苯基和 2-吡啶基取代基，在氮原子上含有苄基或 2-吡啶基取代基。

  DOI：

  10.1007/s11172-013-0131-0
• 作为产物：
  描述：

  benzylphosphine 以 乙醇 为溶剂， 反应 12.0h， 生成 1,5-diphenyl-3,7-dibenzyl-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

文献信息

• Conformational Analysis of P,N‐Containing Eight‐Membered Heterocycles and Their Pt/Ni Complexes in Solution
  作者：Shamil Latypov、Anna Strelnik、Anna Balueva、Yulia Spiridonova、Andrey Karasik、Oleg Sinyashin

  DOI：10.1002/ejic.201501331

  日期：2016.3

  CBCB1* form. In general, distortion of the metal coordination plane and the intramolecular exchange barriers are higher in Ni complexes than in Pt ones. An Ar group at the nitrogen atom increases the heterocycle interconversion rate. Bulky P-substituents increase the distortion of the metal coordination plane and slow down its “twisting” rate. Counterions with stronger coordinating ability increase the barriers

  在溶液中，1,5-二氮杂-3,7-二磷酸环辛烷（PR2NR'2）在冠（CW；主要）和椅船（CB；次要）形式之间处于平衡状态。氮原子上的芳族取代基使平衡向有利于 CW 形式的方向移动。[Pt(PR2NR'2)]Cl2 复合物以 CB (CB*) 构象存在于溶液中，与杂原子上的取代基无关。N 上的芳香取代基显着降低了 CB-CB* 构象交换的障碍。双配体配合物 ([M(PR2NR'2)2]2+, M = Pt, Ni) 为金属配位面扭曲的 CBCB1 构象。CBCB1 形式与 CBCB1* 形式处于退化交换中。一般来说，Ni 配合物的金属配位面畸变和分子内交换势垒高于 Pt 配合物。氮原子上的 Ar 基团增加了杂环相互转化率。庞大的 P 取代基会增加金属配位面的变形并减慢其“扭曲”速率。具有更强配位能力的反离子增加了分子内转化的障碍。
• Synthesis and Structure of Iron (II) Complexes of Functionalized 1,5-Diaza-3,7-Diphosphacyclooctanes
  作者：Yulia S. Spiridonova、Yulia A. Nikolaeva、Anna S. Balueva、Elvira I. Musina、Igor A. Litvinov、Igor D. Strelnik、Vera V. Khrizanforova、Yulia G. Budnikova、Andrey A. Karasik

  DOI：10.3390/molecules25173775

  日期：——

  In order to synthesize new iron (II) complexes of 1,5-diaza-3,7-diphosphacyclooctanes with a wider variety of the substituents on ligands heteroatoms (including functionalized ones, namely, pyridyl groups) and co-ligands, it was found that these ligands with relatively small phenyl, benzyl, and pyridin-2-yl substituents on phosphorus atoms in acetonitrile formed bis-P,P-chelate cis-complexes [L2Fe(CH3CN)2]2+

  为了合成新的 1,5-二氮杂-3,7-二磷杂环辛烷的铁 (II) 配合物，在配体杂原子（包括功能化的杂原子，即吡啶基）和共配体上具有更广泛的取代基，发现这些在乙腈中磷原子上具有相对较小苯基、苄基和吡啶-2-基取代基的配体形成双-P,P-螯合顺式络合物[L2Fe(CH3CN)2]2+ (BF4)2-，而P -mesityl 取代的配体仅形成单配体 P,P-复合物 [LFe(CH3CN)4]2+ ( )2-。3,7-二苄基-1,5-二(1'-(R)-苯乙基)-1,5-二氮杂-3,7-二磷酸环辛烷与四氟硼酸铁 (II) 六水合物在丙酮中反应，得到一种不寻常的双- [L2Fe( )]+ -的配体阳离子络合物，根据 X 射线衍射数据，四氟硼酸盐单元的两个氟原子在大致八面体的铁离子处占据两个伪赤道位置。1,5-二氮杂-3,7-二磷杂环辛烷取代四氢呋喃和环戊二烯基二羰基（四氢呋喃）铁（II）
• Novel iron (II) complexes of 1,5-diaza-3,7-diphosphacyclooctanes
  作者：Irina R. Dayanova、Yulia A. Nikolaeva、Ivan V. Kharyushin、Igor D. Strelnik、Roman M. Khabibullin、Anna S. Balueva、Elvira I. Musina、Andrey A. Karasik

  DOI：10.1080/10426507.2018.1543296

  日期：2019.5.27

  Abstract New cationic octahedral bis-ligand iron (II) complexes of 1,5-diaza-3,7-diphosphacyclooctanes were synthesized as mixtures of two cis-isomers with different mutual arrangement of Fe–P-bonds and co-ligands which may be separated by a fractional crystallization. Graphical Abstract

  摘要 合成了 1,5-二氮杂-3,7-二磷杂环辛烷的新型阳离子八面体双配体铁 (II) 配合物，作为两种具有不同相互排列的 Fe-P 键和共配体的顺式异构体的混合物。通过分级结晶分离。图形概要
• Versatile Synthesis of P^R₂N^R′₂ Ligands for Molecular Electrocatalysts with Pendant Bases in the Second Coordination Sphere
  作者：Michael D. Doud、Kyle A. Grice、Alyssia M. Lilio、Candace S. Seu、Clifford P. Kubiak

  DOI：10.1021/om201168h

  日期：2012.2.13

  Two 1,5-diaza-3,7-diphosphacyclooctane (P2N2) ligands with alkyl-substituted phosphines have been synthesized via a versatile method that allows for improved control of the phosphine substituent. The methyl- and benzyl-substituted phosphine P2N2 ligands ((P2N2Ph)-N-Me and (P2N2Ph)-N-Bn) were synthesized and characterized by P-31H-1} NMR, H-1 NMR, and elemental analysis, and their corresponding [Ni((P2N2Ph)-N-R)(2)](BF4)(2) complexes were synthesized and characterized by P-31H-1) NMR, H-1 NMR, and electrochemistry. The structure of the complex [Ni((P2N2Ph)-N-Me)(2)](CF3SO3)(2) was characterized by X-ray crystallography.
• Studies of a Series of [Ni(P^R₂N^Ph₂)₂(CH₃CN)]²⁺ Complexes as Electrocatalysts for H₂ Production: Substituent Variation at the Phosphorus Atom of the P₂N₂ Ligand
  作者：Uriah J. Kilgore、Michael P. Stewart、Monte L. Helm、William G. Dougherty、W. Scott Kassel、Mary Rakowski DuBois、Daniel L. DuBois、R. Morris Bullock

  DOI：10.1021/ic201461a

  日期：2011.11.7

  A series of [Ni((P2N2Ph)-N-R)(2)(CH3CN)](BF4)(2) complexes containing the cyclic diphosphine ligands [(P2N2ph)-N-R = 1,5-diaza-3,7-diphosphacyclooctane; R = benzyl (Bn), n-butyl (n-Bu), 2-phenylethyl (PE), 2,4,4-trimethylpentyl (TP), and cyclohexyl (Cy)] have been synthesized and characterized. X-ray diffraction studies reveal that the cations of [Ni((P2N2Ph)-N-Bn)(2)(CH3CN)](BF4)(2) and [Ni((P2n-BuN2Ph))(2)(CH3CN)](BF4)(2) have distorted trigonal bipyramidal geometries. The Ni(0) complex [Ni((P2N2Ph)-N-Bn)(2)] was also synthesized and characterized by X-ray diffraction studies and shown to have a distorted tetrahedral structure. These complexes, with the exception of [Ni((P2N2Ph)-N-Cy)(2)(CH3CN)](BF4)(2), all exhibit reversible electron transfer processes for both the Ni (II/I) and Ni(I/0) couples and are electrocatalysts for the production of H-2 in acidic acetonitrile solutions. The heterolytic cleavage of H-2 by [Ni((P2N2Ph)-N-R)(2)(CH3CN)](BF4)(2) complexes in the presence of p-anisidine or p-bromoaniline was used to determine the hydride donor abilities of the corresponding [HNi((P2N2Ph)-N-R)(2)](BF4) complexes. However, for the catalysts with the most bulky R groups, the turnover frequencies do not parallel the driving force for elimination of H-2, suggesting that steric interactions between the alkyl substituents on phosphorus and the nitrogen atom of the pendant amines play an important role in determining the overall catalytic rate.