(+)-1,2-bis(di-o-tolylphosphino)ethane | 50396-26-4

• 物质功能分类: 有机原料 - 有机膦化合物
• 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: (+)-1,2-bis(di-o-tolylphosphino)ethane
• 英文别名: (o-tolyl)2P(CH2)2P(o-tolyl)2；((2-(Me)C6H4)2P(CH2)2P(2-C6H4(Me))2；(o-Tol)2P6(CH2)2P(o-Tol)2；(Ethane-1,2-diyl)bis[bis(2-methylphenyl)phosphane]；2-bis(2-methylphenyl)phosphanylethyl-bis(2-methylphenyl)phosphane
• CAS: 50396-26-4
• 化学式: C₃₀H₃₂P₂
• 分子量: 454.532
• InChiKey: WSKNXSNPDVVYOZ-UHFFFAOYSA-N

物化性质

• 熔点：
  148 °C
• 沸点：
  569.9±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  (+)-1,2-bis(di-o-tolylphosphino)ethane 在 碘 作用下， 以 乙醚 为溶剂， 反应 96.0h， 生成
  参考文献：
  名称：

  固态和溶液中某些二叔和三叔膦的二碘加合物的结构

  摘要：

  一系列二叔膦-四碘加合物R 2 P（I 2）（CH 2）n P（I 2）R 2（R = Ph，n  = 1-4； R = PhCH 2或邻-CH 3 C 6 H 4，n  = 2）和两个三叔膦-己碘加合物PhP（CH 2 CH 2 PPh 2）2 I 6和CH 3 C（CH 2 PPh 2）3 I 6已通过31 P- {H}溶液NMR和拉曼光谱进行了制备和表征。在Ph 2 P（I 2）（CH 2）n P（I 2）Ph 2（n  = 2或4）的情况下，已使用31 P- {H} NMR魔角旋转NMR光谱研究了性质固态的化合物。与我们先前对单膦衍生物R 3 PI 2的广泛研究相一致，四碘二膦化合物Ph 2 P（I 2）（CH 2）n P（I 2）Ph 2 从二乙醚中分离出来的（n = 2或4）包含分子四坐标的磷中心，二碘以线性辐条键合到该中心，如在CDCl 3溶液中获得的31 P- {H} NM

  DOI：

  10.1039/a706277j
• 作为产物：
  描述：

  二-O-二甲苯氯化磷 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成 (+)-1,2-bis(di-o-tolylphosphino)ethane
  参考文献：
  名称：

  Electron Withdrawing Substituents on Equatorial and Apical Phosphines Have Opposite Effects on the Regioselectivity of Rhodium Catalyzed Hydroformylation

  摘要：

  The electronic effects of electron withdrawing aryl substituents on equatorial and apical diphosphines were investigated. Chelating diphosphines designed to coordinate in diequatorial or in apical-equatorial positions were synthesized, and their effects on the regioselectivity of rhodium catalyzed 1-hexene hydroformylation were observed. Only diequatorial coordination was observed for 2,2'-bis[(diphenylphosphino)methyl]-1,1'-biphenyl (BISBI) complexes (BISBI)Ir(CO)(2)H (8) and [BISBI-(3,5-CF3)]Ir(CO)(2)H (10), and only apical-equatorial coordination was seen for 1,2-bis(diphenylphosphino)ethane (DIPHOS) complexes (DIPHOS)Ir(CO)(2)H (14) and [DIPHOS-(3,5-CF3)]Ir(CO)(2)H (15). For the trans-1,2-bis [(diphenylphosphino)methyl] cyclopropane (T-BDCP) complexes, a mixture of diequatorial and apical-equatorial complexes was seen. For (T-BDCP)Ir(CO)(2)H (12), 12-ee was favored over 12-ee by 63:37, but for [T-BDCP-(3,5-CF3)]Ir(CO)(2)H (13) the conformational preference was reversed and a 10:90 ratio of 13-ee:13-ee was seen. The electron withdrawing groups in the equatorial positions of BISBI-(3,5-CF3) (1) and T-BDCP-(3,5-CF3) (2) led to an increase in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation. However, electron withdrawing aryl substituents in the apical positions of DIPHOS-(3,5-CF3) (3) led to a decrease in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation.

  DOI：

  10.1021/ja9719440

文献信息

• New developments in the studies of the reactivity of cyclometallated palladium(II) compounds with homo- ([P,P],[As,As]) and heterobidentate ([P,N],[P,O]) ligands
  作者：Raquel Ares、Margarita López-Torres、Alberto Fernández、Digna Vázquez-García、M. Teresa Pereira、José M. Vila、Leticia Naya、Jesús J. Fernández

  DOI：10.1016/j.jorganchem.2007.06.041

  日期：2007.9

  diarsine ligands in 1:1 molar ratio gave the dinuclear complexes [Pd[RC6H3C(H)NCy-C2,N](Cl)}2μ-(o-Tol)2P(CH2)2P(o-Tol)2}] (R = 4-(COH), 3; R = 5-(COH), 4), [Pd[RC6H3C(H)NCy-C2,N](Cl)}2μ-Ph2PC4H2(NH)CH2PPh2}] (R = 4-(COH), 5; R = 5-(COH), 6) and [Pd[RC6H3C(H)NCy-C2,N](Cl)}2μ-Ph2As(CH2)2AsPh2}] (R = 4-(COH), 7; R = 5-(COH), 8) with the homobidentate [P,P] and [As,As] ligands in a bridging mode. Treatment

  氯桥联双核化合物[Pd [RC 6 H 3 C（H）NCy- C 2，N ]}（μ-Cl）] 2的处理（R = 4-（COH），1 ; R = 5- （COH），2）与摩尔比为1：1的二齿磷或砷二膦或二砷配体得到双核配合物[Pd [RC 6 H 3 C（H）NCy- C 2，N ]（Cl）} 2 μ-（o -Tol）2 P（CH 2）2 P（o -Tol）2 }]（R = 4-（COH），3 ; R = 5-（COH），4），[PD [RC 6 H ^ 3 C（H）NCy- Ç 2，Ñ ]（CL）} 2 μ-PH 2 PC 4 ħ 2（NH）CH 2 PPH 2 }]（R = 4-（ COH），5 ; R = 5-（COH），6）和[PD [RC 6 H ^ 3 C（H）NCy- ç 2，ñ ]（CL）} 2 μ-PH 2如（CH 2）2 AsPh 2 }]（R = 4-（COH），7
• Synthesis, characterization and crystal structures of cyclometallated palladium (II) compounds containing difunctional ligands with [P,P], [As,As], [N,N], [P,As], [P,N] and [P,O] donor atoms
  作者：Raquel Ares、Digna Vázquez-García、Margarita López-Torres、Alberto Fernández、Nina Gómez-Blanco、José M. Vila、Jesús J. Fernández

  DOI：10.1016/j.jorganchem.2008.08.023

  日期：2008.11

  Treatment of the chloro-bridged dinuclear complex [Pd3,4-(MeO)2C6H2C(H)N(Cy)-C6,N}(μ-Cl)]2 (1) with homobidentate [P,P], [As,As], [N,N], and heterobidentate [P,As], [P,N] ligands in a 1:1 molar ratio gave the dinuclear complexes [Pd[3,4-(MeO)2C6H2C(H)N(Cy)-C6,N](Cl)}2μ-L}] (L = Ph2PC4H6(NH)CH2PPh2 (2); Ph2As(CH2)2AsPh2 (3); 1,3-(NH2CH2)2C6H4 (4); Ph2P(CH2)2AsPh2 (5); Ph2P(CH2)2NH2 (6)), with the

  氯桥联双核络合物[Pd 3,4-（MeO）2 C 6 H 2 C（H）N（Cy）-C 6，N }（μ-Cl）] 2（1）的处理为纯正的[ P，P ]，[ As，As ]，[ N，N ]和异双峰[ P，As ]，[ P，N ]配体以1：1的摩尔比得到双核络合物[Pd [3,4- （MeO）2 C 6 H 2 C（H）N（Cy）-C 6，N ]（Cl）}2 μ-L}]（L = Ph 2 PC 4 H 6（NH）CH 2 PPh 2（2）; Ph 2 As（CH 2）2 AsPh 2（3）; 1,3-（NH 2 CH 2）2 C 6 H 4（4）; Ph 2 P（CH 2）2 AsPh 2（5）; Ph 2 P（CH 2）2 NH 2（6）），双齿配体桥接两个环金属化片段。
• Copper(I) Diphosphine Catalysts for C−N Bond Formation: Synthesis, Structure, and Ligand Effects
  作者：Stephen Daly、Mairi F. Haddow、A. Guy Orpen、Giles T. A. Rolls、Duncan F. Wass、Richard L. Wingad

  DOI：10.1021/om800139v

  日期：2008.7.1

  chelating ligand. The complexes have been screened for catalytic amidation reactions. Although in most cases only very low activity is observed, comparable with simple copper halide salts, notable exceptions are catalysts based on N,N-bis(diphenylphosphino)amine ligands, where a significant improvement in catalyst efficiency is observed. We propose the unusual electronic properties of these ligands may be

  一系列含有双（二芳基膦基）丙烷，双（二芳基膦基）乙烷，双（二芳基膦基）甲烷和N，N-双（二芳基膦基）胺配体的铜（I）配合物（芳基= Ph，2-C 6 H 4（ Me）或2-C 6 H 4（i -Pr））已合成。报道了所选氯化物衍生物的晶体结构。事实证明，该复杂结构对螯合配体的主链和P-取代基都非常敏感。已经针对催化酰胺化反应筛选了配合物。尽管在大多数情况下仅观察到非常低的活性，与简单的卤化铜盐相比，值得注意的例外是基于N，N的催化剂-双（二苯基膦基）胺配体，其中观察到催化剂效率的显着改善。我们提出这些配体的不同寻常的电子性能可能是它们在先前已使用硬供体配体的这些和其他催化反应中表现出不同性能的原因。
• Rhodium-Catalyzed Branched-Selective Alkyne Hydroacylation: A Ligand-Controlled Regioselectivity Switch
  作者：Carlos González-Rodríguez、Rebekah J. Pawley、Adrian B. Chaplin、Amber L. Thompson、Andrew S. Weller、Michael C. Willis

  DOI：10.1002/anie.201100956

  日期：2011.5.23

  It's all in the ligand: By choice of the appropriate diphosphine ligand a previously linear‐selective alkyne hydroacylation process can be “switched” to be highly branched‐selective (see scheme, l=linear, b=branched). Structural data for the ortho‐iPr‐dppe–rhodium catalyst suggest restricted rotation of the phosphine aryl units may be responsible for the observed selectivity.

  全部都在配体中：通过选择合适的二膦配体，可以将先前的线性选择性炔烃加氢酰化过程“切换”为高度支化的选择性（参见方案，l =线性，b =分支）。用于结构数据邻-我镨DPPE-铑催化剂建议限制膦芳基单元的旋转可以是负责观察到的选择性。
• The preparation and properties of some diphosphines R2PCH2CH2PR2(R = alkyl or aryl) and of their rhenium(I) dinitrogen derivatives
  作者：Joseph Chatt、Wasif Hussain、G. Jeffery Leigh、Hapipah Mohd. Ali、Christopher J. Picket、Douglas A. Rankin

  DOI：10.1039/dt9850001131

  日期：——

  The synthesis of a range of diphosphines R2PCH2CH2PR2 from Cl2PCH2CH2PCl2 is described. The properties of a series of complexes [ReCl(N2)(R2PCH2CH2PR2)2] derived from them are discussed. The relationship between the values of E½ox and ν(N2) for the complexes suggests that electron-withdrawing substituents on the diphosphine upset the usual balance of σ and π effects in rhenium–dinitrogen bonding.

  描述了从Cl 2 PCH 2 CH 2 PCl 2合成一定范围的二膦R 2 PCH 2 CH 2 PR 2。讨论了从它们衍生的一系列配合物[ReCl（N 2）（R 2 PCH 2 CH 2 PR 2）2 ]的性质。的值之间的关系Ë ½牛和ν（N 2），用于所述配合物表明在二膦即吸电子取代基打乱σ和铼二氮键合π作用的通常的平衡。