cis-[Pd(SO4)(PPh3)2] | 15227-23-3

• 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: cis-[Pd(SO4)(PPh3)2]
• 英文别名: cis-Pd(SO4)(PPh3)2；palladium(2+);triphenylphosphane;sulfate
• CAS: 15227-23-3
• 化学式: C₃₆H₃₀O₄P₂PdS
• 分子量: 727.065
• InChiKey: JVURYMJWVOCXAN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.08
• 重原子数：
  44.0
• 可旋转键数：
  8.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  sulfur dioxide-bis(triphenylphosphane)-palladium(0) 在 氧气 作用下， 以 苯 为溶剂， 生成 cis-[Pd(SO4)(PPh3)2]
  参考文献：
  名称：

  Hoffmann, Th.; Hoffmann, H.; Karabit, M., Zeitschrift fur Anorganische und Allgemeine Chemie

  摘要：

  DOI：
• 作为试剂：
  描述：

  甲醇 、 乙烯 、 一氧化碳 在 cis-[Pd(SO4)(PPh3)2] 、 对苯醌 作用下， 55.0 ℃ 、5.07 MPa 条件下， 反应 1.0h， 生成 草酸二甲酯 、 碳酸二甲酯
  参考文献：
  名称：

  Oxidative carbonylation of ethene catalyzed by Pd(II)–PPh3 complexes in MeOH using benzoquinone as stoichiometric oxidant

  摘要：

  The complexes [Pd(COOMe)nX(2-n)(PPh3)(2)] (n=0, 1, 2; X =TsO, OAc, ONO2, Cl, Br). [Pd(SO4)(PPh3)](2), [PdCl2(PPh3)](2) and PdX2 (X = Cl, Br, I) catalyze the oxidative ethene carbonylation in MeOH using benzoquinone (BQ) as stoichiometric oxidant. The main products dimethyl succinate (DMS) and dimethyl oxalate (DMO) are formed together with minor amounts of methyl propanoate and dimethyl carbonate. The formation of DMS unambiguously proves that ethene inserts into a Pd-COOMe bond. The influence of the CO/ethene ratio at constant total pressure and of the BO/Pd ratio on the product distribution has been studied. Model reactions of a Pd-hydride with BQ of trans-[Pd(COOMe)(TsO)(PPh3)(2)] with ethene in the presence of BQ and of trans-[Pd(COOMe)(2)(PPh3)(2)] with BQ have been studied by P-31{H-1} NMR. BQ consumes the Pd-hydride and directs the catalysis toward a Pd-COOMe initiator leading to DMS. In the catalysis to DMO. BQ is likely to favour the formation of a Pd-{COOMe}(2) species having the two carbomethoxy ligands in vicinal position such to favour the elimination of the product. The proposed catalytic cycles for the formation of the products are discussed. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2011.10.013

文献信息

• Efficient oxidative carbonylation of PrOH to oxalate catalyzed by Pd(II)–PPh3 complexes using benzoquinone as a stoichiometric oxidant
  作者：E. Amadio、L. Toniolo

  DOI：10.1016/j.jorganchem.2014.05.033

  日期：2014.9

  before the β-H elimination. Instead there is a nucleophilic intrasphere attack of the alkoxy ligand onto a CO ligand. After catalysis the precursor trans-[PdBr2(PPh3)2] has been detected, together with trans-[PdBr(COOiPr)(PPh3)2] and [Pd(BQ)(PPh3)2]. PPh3 remains coordinated to the palladium centre during catalysis. A BQ- and halides-assisted catalytic cycle is proposed. In this cycle, the reoxidation

  反式-[PdBr 2（PPh 3）2 ] / NEt 3 / PPh 3 / LiBr的催化体系在i PrOH氧化羰基化为相应的草酸盐中具有很高的活性，并具有选择性，该苯甲酸是用苯醌（BQ）作为化学计量的氧化剂。草酸盐与少量的碳酸盐和丙酮一起形成。讨论了催化体系中各组分的影响以及BQ浓度，反应时间，温度和CO压力的影响。NEt 3中和在催化循环中释放的酸，因此有利于二碳烷氧基中间体的形成。新增PPh 3与苯醌反应生成甜菜碱，甜菜碱是有助于进一步提高催化活性的碱。该溴-阴离子可能坐标，其在所形成的钯（0）的产物形成步骤从而稳定其对分解和使其再氧化更容易和重新进入催化循环。催化活性仅取决于BQ的浓度，这表明未配位的BQ不参与催化循环的缓慢步骤，或者这些物种中BQ的配位强烈。随着NEt 3和PPh 3浓度的增加，对草酸盐的催化活性增加。，而对碳酸盐的选择性和丙酮的形成几乎保持不变。除了抑制丙酮的
• Heyke, O.; Neher, A.; Lorenz, I.-P., Zeitschrift fur Anorganische und Allgemeine Chemie
  作者：Heyke, O.、Neher, A.、Lorenz, I.-P.

  DOI：——

  日期：——