1,5-di(p-methoxyphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane | 1291071-43-6

• 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: 1,5-di(p-methoxyphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane
• 英文别名: 1,5-di(4-methoxyphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane；1,5-Bis(4-methoxyphenyl)-3,7-diphenyl-1,5,3,7-diazadiphosphocane；1,5-bis(4-methoxyphenyl)-3,7-diphenyl-1,5,3,7-diazadiphosphocane
• CAS: 1291071-43-6
• 化学式: C₃₀H₃₂N₂O₂P₂
• 分子量: 514.544
• InChiKey: ZNOSQYBKVKPRDS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  24.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate 、 1,5-di(p-methoxyphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane 以 乙腈 为溶剂， 反应 4.0h， 以95%的产率得到C₃₇H₄₀N₃O₂P₂Ru⁽¹⁺⁾*F₆P^(1-)
  参考文献：
  名称：

  催化剂下垂基对炔基胺环化的影响

  摘要：

  制备了一个[CpRu（PP）（MeCN）] PF 6配合物（2 a – e和4），其中双膦配体在第二配位领域包含一个侧基叔胺。2 - ë含有P博士2 Ñ R' 2点具有两个胺基团作为侧基的配体。配合物4具有仅具有一种侧胺的P Ph 2 N Ph 1配体。2 a – e和4的催化性能在2-乙炔基苯胺和2-乙炔基苄醇的环化中进行了评估。已经发现，侧链胺在金属活性位点附近的定位对于高催化剂性能是必不可少的。P的比较博士2 Ñ R' 2种催化剂（2 - ë）显示性能最小差作为侧胺碱度的函数。而是，仅需要阈值碱度（其中的侧链胺比底物更碱性）即可实现高性能。

  DOI：

  10.1002/cctc.201800713
• 作为产物：
  描述：

  苯基膦 以 乙醇 为溶剂， 反应 2.08h， 生成 1,5-di(p-methoxyphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane
  参考文献：
  名称：

  Electrocatalytic Oxidation of Formate by [Ni(P^R₂N^R′₂)₂(CH₃CN)]²⁺ Complexes

  摘要：

  [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.

  DOI：

  10.1021/ja204489e

文献信息

• 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+ (BF4)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(BF4)]+BF4-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）
• [Ni(P^Ph₂N^C6H4X₂)₂]²⁺Complexes as Electrocatalysts for H₂Production: Effect of Substituents, Acids, and Water on Catalytic Rates
  作者：Uriah J. Kilgore、John A. S. Roberts、Douglas H. Pool、Aaron M. Appel、Michael P. Stewart、M. Rakowski DuBois、William G. Dougherty、W. Scott Kassel、R. Morris Bullock、Daniel L. DuBois

  DOI：10.1021/ja109755f

  日期：2011.4.20

  as overpotentials are decreased. Catalytic studies using acids with a range of pK(a) values reveal that turnover frequencies do not correlate with substrate acid pK(a) values but are highly dependent on the acid structure, with this effect being related to substrate size. Addition of water is shown to dramatically increase catalytic rates for all catalysts. With [Ni(P(Ph)(2)N(C6H4CH2P(O)(OEt)2)(2))(2)](BF(4))(2)

  一系列单核镍(II)双(二膦)配合物[Ni(P(Ph)(2)N(C6H4X)(2))(2)](BF(4))(2) (P(Ph)( 2)N(C6H4X)(2) = 1,5-di(para-X-phenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane；X = OMe, Me, CH(2 )P(O)(OEt)(2)、Br 和 CF(3)) 已被合成和表征。X 射线衍射研究表明 [Ni(P(Ph)(2)N(C6H4Me)(2))(2)](BF(4))(2) 和 [Ni(P(Ph)(2)N (C6H4OMe)(2))(2)](BF(4))(2) 是具有扭曲方形平面几何形状的四坐标。每个配合物的 Ni(II/I) 和 Ni(I/0) 氧化还原对在乙腈中是电化学可逆的，随着 X 给电子特性的增加，其阴极电位越来越高。这些配合物中的每一种都是在 Ni(II/I)
• 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.
• Catalyst Pendent-Base Effects on Cyclization of Alkynyl Amines
  作者：James M. Stubbs、Devon E. Chapple、Paul D. Boyle、Johanna M. Blacquiere

  DOI：10.1002/cctc.201800713

  日期：2018.9.7

  A family of [CpRu(PP)(MeCN)]PF6 complexes (2 a–e and 4) were prepared in which the bis‐phosphine ligand contains a pendent tertiary amine in the second‐coordination sphere. 2 a–e contain PPh2NR′2 ligands with two amine groups as the pendent base. Complex 4 has the PPh2NPh1 ligand with only one pendent amine. The catalytic performance of 2 a–e and 4 were assessed in the cyclization of 2‐ethynyl aniline

  制备了一个[CpRu（PP）（MeCN）] PF 6配合物（2 a – e和4），其中双膦配体在第二配位领域包含一个侧基叔胺。2 - ë含有P博士2 Ñ R' 2点具有两个胺基团作为侧基的配体。配合物4具有仅具有一种侧胺的P Ph 2 N Ph 1配体。2 a – e和4的催化性能在2-乙炔基苯胺和2-乙炔基苄醇的环化中进行了评估。已经发现，侧链胺在金属活性位点附近的定位对于高催化剂性能是必不可少的。P的比较博士2 Ñ R' 2种催化剂（2 - ë）显示性能最小差作为侧胺碱度的函数。而是，仅需要阈值碱度（其中的侧链胺比底物更碱性）即可实现高性能。
• 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.