2,6-bis[(di-t-butylphosphino)methyl]phenyl palladium trifluoroacetate | 210363-39-6

• 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: 2,6-bis[(di-t-butylphosphino)methyl]phenyl palladium trifluoroacetate
• 英文别名: Pd(trifluoroacetate)((1,3-bis[(di-tert-butylphosphino)methyl]benzene)(-1H))；Pd(trifluoroacetate)[2,6-(tBu2PCH2)2C6H3]；Pd(TFA)[2,6-(tBu2PCH2)2C6H3]；Pd(TFA)(C6H3(CH2P(t-Bu)2)2)
• CAS: 210363-39-6
• 化学式: C₂₆H₄₃F₃O₂P₂Pd
• 分子量: 612.989
• InChiKey: FMQOIWLCEOYNPY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  2,6-bis[(di-t-butylphosphino)methyl]phenyl palladium trifluoroacetate 在 2,2'-bipyridyl 作用下， 以 四氢呋喃 、 氘代苯 、 甲苯 为溶剂， 生成 (2,6-bis[(di-tert-butylphosphino)methyl]phenyl)Pd(O2COH)
  参考文献：
  名称：

  CO 2插入（PCP）烯丙基钯和甲基σ键的机理。动力学和计算研究

  摘要：

  的σ键合的（PCP）的反应的Pd-ME络合物（PCP = 2,6-双[（二-叔-butylphosphino）甲基]苯基）与CO 2是一阶在钯和一阶中的CO 2用速率常数ķ小号= 8.9±0.8摩尔-1小号-1在353个K.激活参数Δ ħ ⧧ = 73±7千焦/摩尔和Δ小号⧧ = -118±19 J / K摩尔。基于此和理论计算，我们提出了一种S E 2机理，其中配位甲基在双分子反应中攻击完全不配位的二氧化碳分子。PCPPd-巴豆基复合物是在65:35 E下合成的：Z混合物，并显示它与CO 2反应，得到复杂的PCPPd-O（CO）CH（CH 3）CHCH 2为单一异构体，其中前一个γ-碳已被羧化。理论计算再次表明一个S ë 2机构与noncoordinated二氧化碳与在烯丙基的末端碳反应，形成η 2键合的烯烃络合物作为中间体。该中间体到O键合产物的重排被认为是决定速率的。报道了PCPPd-O（CO）C（CH

  DOI：

  10.1021/om100325v
• 作为产物：
  描述：

  在 H₂ 作用下， 以 甲苯 为溶剂， 以55%的产率得到2,6-bis[(di-t-butylphosphino)methyl]phenyl palladium trifluoroacetate
  参考文献：
  名称：

  Alkyl− and Aryl−Oxygen Bond Activation in Solution by Rhodium(I), Palladium(II), and Nickel(II). Transition-Metal-Based Selectivity

  摘要：

  Reaction of [RhCl(C8H14)(2)](2) (C8H14 = cyclooctene)with 2 equiv of the aryl methyl ether phosphine 1 in C6D6 results in an unprecedented metal insertion into the strong sp(2)-sp(3) aryl-O bond. This remarkable reaction proceeds even at room temperature and occurs directly, with no intermediacy of C-H activation or insertion into the adjacent weaker ArO-CH3 bond. Two new phenoxy complexes (8 and 9), which are analogous to the product of insertion into the ArO-CH3 bond (had it taken place) were prepared and shown not to be intermediates in the Ar-OCH3 bond cleavage process. Thus, aryl-O bond activation by the nucleophilic Rh(I) is kinetically preferred over activation of the alkyl-O bond. The phenoxy Rh(I)-eta(1)-N-2 complex (8) is in equilibrium with the crystallographically characterized Rh(I)-mu-N-2-Rh(I) dimer (12). Reaction of [RhCl(C8H14)(2)](2) With 2 equiv of the aryl methyl ether phosphine 2, PPh3, and excess HSiR3 (R = OCH2CH3, CH2CH3) results also in selective metal insertion into the aryl-O bond and formation of (CH3O)SiR3. Thus, transfer of a OCH3 group from carbon to silicon was accomplished, showing that hydrosilation of an unstrained aryl-O single bond by a primary silane is possible. The selectivity of C-O bond activation is markedly dependent on the transition-metal complex and the alkyl group involved, allowing direction of the C-O bond activation process at either the aryl-O or alkyl-O bond. Thus, contrary to the reactivity of the rhodium complex, reaction of NiI2 or Pd(CF3CO2)(2) with 1 equiv of 1 in ethanol or C6D6 at elevated temperatures results in exclusive activation of the sp(3)-sp(3) ArO-CH3 bond, while reaction of the analogous aryl ethyl ether 4 and Pd(CF3CO2)(2) results in both sp(3)-sp(3) and sp(2)-sp(3) C-O bond activation. The resulting phenoxy Pd(II) complex (18) is fully characterized by X-ray analysis. Heating the latter under mild dihydrogen pressure results in hydrodeoxygenation to afford an aryl-Pd(II) complex (19).

  DOI：

  10.1021/ja9738889
• 作为试剂：
  描述：

  二氧化碳 、 Dimethylzinc 在 2,6-bis[(di-t-butylphosphino)methyl]phenyl palladium trifluoroacetate 作用下， 以 苯 为溶剂， 生成 zinc diacetate
  参考文献：
  名称：

  Insertion of Carbon Dioxide into (PCP)Pd^II−Me Bonds

  摘要：

  A (PCP)PdMe complex has been synthesized and structurally characterized, displaying a very long Pd-Me bond. It is reactive toward CO2 insertion, giving the corresponding acetate in quantitative yield. The methyl complex can be regenerated using ZnMe2, and catalytic carboxylation is possible in benzene.

  DOI：

  10.1021/om0505561

文献信息

• Insertion of CO₂into a palladiumallyl bond and a Pd(<scp>ii</scp>) catalysed carboxylation of allyl stannanes
  作者：Roger Johansson、Ola F. Wendt

  DOI：10.1039/b614037h

  日期：——

  henyl allyl palladium (PCPtBuPd-allyl, 3) reacts with CO2 in a very fast insertion reaction to give the corresponding butenoate complex. The reaction is thought to occur via a cyclic six-membered transition state (7), where the γ-carbon of the allyl group is linked up with the CO2-carbon. A group of related PCP complexes were investigated as catalysts for the carboxylation of tributyl(allyl)stannane

  复杂的2,6-双[（二叔丁基膦基）甲基]苯基烯丙基钯（PCP tBu Pd-烯丙基，3）与CO 2的反应非常快插入反应 给相应的 丁烯酸复杂的。该反应被认为是通过环状六元过渡态（7）发生的，其中烯丙基与CO 2-碳相连。一组相关的PCP配合物被调查为催化剂 用于羧化 三丁基（烯丙基）锡烷。提出了用于该反应的催化循环，其中速率确定步骤是锡和钯之间的金属转移。使用较少的空间拥挤，羧化反应更快催化剂钯配合物的电子富集度对反应活性似乎不太重要。因此，2，6-双[（二苯基膦基）甲基]苯基三氟乙酸钯（13）与间苯二酚双（二苯基）次膦酸酯之间的反应性没有明显差异。三氟乙酸钯（10）。这两种络合物都为羧甲基化的羧化提供了高周转率三丁基（烯丙基）锡烷（使用约5％的催化剂负载量和4 atm CO 2压力在16小时内达到80％）。另一方面，配合物3在催化羧化反应中没有活性。
• Synthesis and characterization of fluorophenylpalladium pincer complexes: electronic properties of some pincer ligands evaluated by multinuclear NMR spectroscopy and electrochemical studies
  作者：Alexey V. Polukeev、Sergey A. Kuklin、Pavel V. Petrovskii、Svetlana M. Peregudova、Alexander F. Smol'yakov、Fedor M. Dolgushin、Avthandil A. Koridze

  DOI：10.1039/c1dt10446b

  日期：——

  reaction of LiAr (Ar = C6H4F-4) with the respective trifluoroacetate palladium pincer complexes 9–12. The molecular structures of 14 and 16 were determined by an X-ray crystallographic method. Complexes 13–16 and Pd(Ar)[2,5-(tBu2PCH2)2C5H2}Fe(C5H5)]}PF6 (17) were studied by multinuclear NMR spectroscopy and cyclic voltammetry. On the basis of 19F NMR chemical shifts and 1J(13C–19F) coupling constants,

  具有不同钳位配体的钯氟苯基配合物Pd（Ar）[2,6-（t Bu 2 PCH 2）2 C 6 H 3 ]（13），Pd（Ar）[2,6-（t Bu 2 PO）2 C 6 H 3 ]（14），Pd（Ar）[2,5-（t Bu 2 PCH 2）2 C 5 H 2 } Fe（C 5 H 5）]（15）和Pd（Ar）[ 2,5-（t Bu 2 PCH 2）2 C 5 H 2 } Ru（C 5 H 5）]（16）是通过LiAr（Ar = C 6 H 4 F-4）与相应的三氟乙酸钯钯夹杂物9-12反应合成的。通过X射线晶体学方法确定14和16的分子结构。配合物13–16和Pd（Ar）[2,5-（t Bu 2 PCH 2）2 C 5 H 2 } Fe（C 5 H 5）]} PF 6（17）用多核NMR光谱和循环伏安法研究。基于19 F NMR化学位移和1 J（13 C– 19 F）耦合常数，以及Pd