Pd(Me)(MeCN)((R,S)-C10H6(PPh2)C10H6OPO2(C10H6)2) | 168330-97-0

• 英文名称: Pd(Me)(MeCN)((R,S)-C10H6(PPh2)C10H6OPO2(C10H6)2)
• 英文别名: (SP-4-3)-Pd(CH3)(CH3CN)[(R,S)-BINAPHOS]*[B(3,5-(CF3)2C6H3)4]；[Pd(Me)(MeCN)((R,S)-BINAPHOS)]*[B(3,5-(CF3)2C6H3)4]
• CAS: 168330-97-0
• 化学式: C₃₂H₁₂BF₂₄*C₅₅H₄₀NO₃P₂Pd
• 分子量: 1794.51
• InChiKey: VQHMVUIOSWDPOZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Pd(Me)(MeCN)((R,S)-C10H6(PPh2)C10H6OPO2(C10H6)2) 、 一氧化碳 以 氘代氯仿 为溶剂， 生成 Pd(COCH3)(CH3CN)((R,S)-C10H6(PPh2)C10H6OPO2(C10H6)2)
  参考文献：
  名称：

  不对称膦-亚磷酸酯配体Pd(II)配合物催化丙烯与一氧化碳交替共聚的机理

  摘要：

  负责丙烯与一氧化碳的高度对映选择性不对称共聚的反应步骤，由带有不对称手性双齿膦-亚磷酸酯的阳离子 Pd(II) 配合物催化，(R,S)-BINAPHOS [(R,S)-2-( diphenylphosphino)-1,1'-binaphthalen-2'-yl 1,1'-binaphthalene-2,2'-diyl phosphite = L1]。对催化剂前体 (SP-4-2)- 和 (SP-4-3)-Pd(CH3)Cl(L1) (1a 和 1b) 和 (SP-4-3)-[ Pd(CH3)(CH3CN)(L1)]·X1 (X1 = B{3,5-(CF3)2C6H3}4) (2)，以及与反应步骤相关的配合物，(SP-4-3)-[ Pd(COCH3)(CH3CN)(L1)]·X1 (3), (SP-4-3)- 和 (SP-4-4)-[Pd{CH2CH(CH3)COCH3}(L1)]·X1 (

  DOI：

  10.1021/ja973199x
• 作为产物：
  描述：

  (SP-4-2)-Pd(CH3)Cl[(R,S)-BINAPHOS] 、 四(3,5-二(三氟甲基)苯基)硼酸钠 、 乙腈 以 二氯甲烷 为溶剂， 生成 Pd(Me)(MeCN)((R,S)-C10H6(PPh2)C10H6OPO2(C10H6)2)
  参考文献：
  名称：

  氟烯烃与一氧化碳交替共聚

  摘要：

  钯催化的氟烯烃交替共聚，表示为 CH(2)=CH-CH(2)-C(n)F(2n+1)，使用 (R,S)-BINAPHOS (2e) 作为配体。CH(2)-C(n)F(2n+1) 基团是迄今为止报道的共聚反应中电负性最强的取代基（CH(2)CF(3) 的 Taft sigma 值为 0.90）。由CH(2)=CH-CH(2)-C(8)F(17)(1a)得到的共聚物以聚螺酮和聚酮的混合物存在，而由CH(2)=CH-CH(2)得到的共聚物-C(4)F(9) (1b) 是一种纯 polyspiroketal，如红外和 (13)C-CP/MAS NMR 光谱所揭示的那样。通过 MALDI-TOF MS 光谱法确认了来自 1b 的聚合物的末端结构。详细的 NMR 研究表明，与 (R,S)-BINAPHOS (2e) 的反应性比与常规配体 DPPP (2a) 的反应性高得多可归因于独特的 1, 2-将氟烯烃插入到酰基钯物种中。在

  DOI：

  10.1021/ja055862k

文献信息

• Cyclocopolymerization of<i>α</i>,<i>ω</i>-Dienes with Carbon Monoxide Catalyzed by (<i>R</i>,<i>S</i>)-BINAPHOS–Pd(II)
  作者：Kyoko Nozaki、Naomasa Sato、Koji Nakamoto、Hidemasa Takaya

  DOI：10.1246/bcsj.70.659

  日期：1997.3

  Cyclocopolymerization of 1,4-pentadiene with carbon monoxide gave polyketone 3 in the presence of a Pd(II) catalyst bearing an unsymmetrical bidentate ligand, (R,S)-BINAPHOS =(R)-2-(diphenylphosphino)-1,1′-binaphthalen-2′yl (S)-1,1′-binaphthalene-2,2′-diyl phsophite}. In the repeating unit of 3, exclusive formation of a cyclopentanone framework rather than cyclohexanone has been revealed by 13C NMR and IR spectroscopies. A single-unit analog 2 was prepared to identify the structure of 3. In the cyclopentanone unit of 3, the two substituents are cis and trans to each other in almost 1 : 1 ratio. The polymer 3 showed different behavior in thermal analysis from that of propene–CO alternating copolymer. 1,5-Hexadiene also afforded the corresponding cyclocopolymer 5. The molar optical rotation of polymer 3 was much lower than that of 5.

  1,4-戊二烯与一氧化碳在带有不对称二齿配体 (R,S)-BINAPHOS =(R)-2-(二苯基膦)-1 的 Pd(II) 催化剂存在下环共聚得到聚酮 3， 1′-联萘-2′基(S)-1,1′-联萘-2,2′-亚磷酸二酯}。 13C NMR和IR光谱表明，在3的重复单元中，仅形成环戊酮骨架而不是环己酮。制备单单元类似物2来鉴定3的结构。在3的环戊酮单元中，两个取代基彼此为顺式和反式，比例几乎为1:1。聚合物3在热分析中表现出与丙烯-CO交替共聚物不同的行为。 1,5-己二烯也得到相应的环共聚物5。聚合物3的摩尔旋光度远低于5。
• High-Pressure NMR Studies on the Alternating Copolymerization of Propene with Carbon Monoxide Catalyzed by a Palladium(II) Complex of an Unsymmetrical Phosphine−Phosphite Ligand
  作者：Kyoko Nozaki、Tamejiro Hiyama、Smita Kacker、István T. Horváth

  DOI：10.1021/om990985x

  日期：2000.5.1

  S)-BINAPHOS; Ar = 3,5-(CF3)2C6H3) to the more stable SP-4-3 isomer (8b) is faster than CO insertion into either 8a or 8b, the CO insertion being reversible. (2) For the PdII−L1-catalyzed copolymerization of propene and CO, there exist at least two major resting states, most probably acylpalladium, (SP-4-3)-[Pd(COR)(L2)(L1)][BAr4] (3; L2 = CH3CN, CO), and alkylpalladium, [PdCH2CH(CH3)C(O)R}(L1)][BAr4]

  当采用高压NMR技术时，揭示了以下两个事实。（1）（SP -4-4）-[Pt（CH 3）（CO）（L 1）] [BAr 4 ]（8a ; L 1 =（R，S）-BINAPHOS; Ar ＝ 3，5-（CF 3）2 C 6 H 3）到更稳定的SP -4-3异构体（8b）比CO插入8a或8b的速度快，CO插入是可逆的。（2）对于Pd II -L 1丙烯和CO的催化共聚反应，至少存在两个主要的静止状态，最可能是酰基铝（（SP -4-3）-[Pd（COR）（L 2）（L 1）] [BAr 4 ]（3 ; L 2＝ CH 3 CN，CO）和烷基钯，[Pd CH 2 CH（CH 3）C（O）R}（L 1）] [BAr 4 ]（5a）。
• Asymmetric terpolymerization of styrene or its derivative and aliphatic 1-alkenes with CO catalyzed by Pd–(R,S)-BINAPHOS
  作者：Yasutoyo Kawashima、Kyoko Nozaki、Tamejiro Hiyama

  DOI：10.1016/s0020-1693(02)01542-6

  日期：2003.7

  Asymmetric terpolymerization of aliphatic 1-alkenes, vinylarenes and carbon monoxide has been studied using Pd-(R,S)-BINAPHOS complex as a catalyst. The glass transition temperature is changeable and dependent on the content of each olefin unit. The terpolymers synthesized by Pd-(R,S)-BINAPHOS system consist of higher I-alkene content, the fact being in sharp contrast to the results with Pd-nitrogen ligand systems. The incorporation degree of [4-tert-butylstyrene-CO] unit in the terpolymer was much lower than that of [1-alkenes-CO] although the insertion of 4-tert-butylstyrene into acetyl-Pd was faster than 1-alkenes. (C) 2003 Elsevier Science B.V. All rights reserved.
• Alternating copolymerization of &lt;FONT FACE="SYMBOl"&gt;w&lt;/FONT&gt;-perfluoroalkyl-1-alkenes with carbon monoxide catalyzed by homogeneous and polymer-supported Pd-complexes
  作者：Kyoko Nozaki、Fumitoshi Shibahara、Stephan Elzner、Tamejiro Hiyama

  DOI：10.1139/cjc-79-5-6-593

  日期：——

  Alternating copolymerization of fluorinated olefins (CnF2n + 1)(CH2)(m)CH=CH2 (1) and carbon monoxide was carried out using cationic Pd(II)-(R,S)-BINAPHOS complexes (2) as catalysts. To obtain polymeric products sufficiently, existence of at least two methylenes in 1 were essential (m greater than or equal to 2). The products thus obtained formed polyspiroketal (4) rather than polyketone (3), the structures being determined by solid- and solution-state NMR and IR analyses. The water contact angle was 108 degrees for a sample of 4f when it was casted on a glass surface from C6F6 solution.