(methoxycarbonyl)(tosyloxy)bis(triphenyl-l⁵-phosphanyl)palladium | 771476-65-4

• 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: (methoxycarbonyl)(tosyloxy)bis(triphenyl-l⁵-phosphanyl)palladium
• 英文别名: trans-[Pd(COOMe)(OTs)(PPh₃)₂]；trans-[Pd(COOMe)(TsO)(PPh₃)₂]；trans-[Pd(OTs)(carbomethoxy)(triphenylphosphine)2]；trans-[Pd(COOCH3)(p-toluenesulfonate)(PPh3)2]；trans-[Pd(COOCH3)(TsO)(PPh3)2]；trans-Pd(COOMe)(TsO)(PPh3)2
• CAS: 771476-65-4
• 化学式: C₄₅H₄₀O₅P₂PdS
• 分子量: 861.243
• InChiKey: WEHHSGMFOBPNOX-UHFFFAOYSA-M

计算性质

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

反应信息

• 作为反应物：
  描述：

  (methoxycarbonyl)(tosyloxy)bis(triphenyl-l⁵-phosphanyl)palladium 在 N(C₂H₅)3 作用下， 以 甲醇 、 二氯甲烷-D2 、 水 为溶剂， 生成 trans-[Pd(COOMe)₂(PPh₃)₂]
  参考文献：
  名称：

  [Pd（COOMe）n X 2− n（PPh 3）2 ]（n = 0，1，2; X = Cl，NO 2，ONO 2，OAc和OTs）在甲醇的氧化羰基化反应中的催化性能

  摘要：

  顺式-[Pd（ONO 2）2（PPh 3）2 ]（1）在吡啶（py）存在下，在温和条件下与CO在甲醇（MeOH）中反应，生成反式-[Pd（COOMe）（ONO 2） （PPh 3）2 ]（1a）。使用NEt 3代替py可以得到1a，反式-[Pd（COOMe）2（PPh 3）2 ]（2）和[Pd（CO）（PPh 3）3 ]的混合物。通过反应制备纯2顺式-[Pd（OTs）2（PPh 3）2 ]，在MeOH中加入一氧化碳，然后加入NEt 3。通过使反式-[Pd（COOMe）Cl（PPh 3）2 ]与AgNO 2或与AgOTs和NaNO 2反应制备硝基络合物反式-[Pd（COOMe）（NO 2）（PPh 3）2 ]（3a）。。1和反式-[Pd（NO 2）2（PPh 3）2 ]（3的新合成）也有报道。所有配合物均已通过IR和1 H和31 P { 1 H} NMR光谱进行了表征。配合物1和2不可逆地定

  DOI：

  10.1021/ic901569w
• 作为产物：
  描述：

  trans-[Pd(COOMe)₂(PPh₃)₂] 、 对甲苯磺酸 在 一氧化碳 作用下， 以 甲醇 、 二氯甲烷-D2 为溶剂， 生成 (methoxycarbonyl)(tosyloxy)bis(triphenyl-l⁵-phosphanyl)palladium
  参考文献：
  名称：

  Mechanistic studies on the selective oxidative carbonylation of MeOH to dimethyl oxalate catalyzed by [Pd(COOMe)n(TsO)2−n(PPh3)2] (n = 0, 1, 2) using p-benzoquinone as a stoichiometric oxidant

  摘要：

  The reactivity of the complexes cis-[Pd(OTs)(2)(PPh3)(2)] (I), trans-[Pd(COOMe)(OTs)(PPh3)(2)] (II) and trans-[(COOMe)(2)(PPh3)(2)] (III), regarding the catalytic oxidative carbonylation of MeOH to dimethyl oxalate (DMO) using benzoquinone (BQ) as a stoichiometric oxidant, has been studied in CD2Cl2/MeOH (10/1, v/v) by H-1 and P-31{H-1} NMR spectroscopy. I reacts with CO and MeOH at 193 K giving II, which is transformed into III upon addition of a base. The same occurs in the presence of BQ. Instead, if the base is added before admission of CO, [Pd(BQ)(PPh3)(2)] is formed. Starting also from II, complex III is formed only after addition of a base. The base neutralizes TsOH which is formed in the transformation of I to II and III. III is unstable in the presence of 1 equivalent of TsOH and it is transformed into II. At 333 K, under 0.4 MPa of CO, III decomposes with formation of DMO and dimethyl carbonate (DMC) (15%) each), whereas, in the presence of BQ, III is unstable already at 298 K, with formation of only DMO (10%). Catalysis to DMO is observed at 333 K. Thus BQ enhances the reactivity of III and directs the catalysis selectively to DMO.I, II and III have also been used in catalytic experiments in pure MeOH at 298 K, under 0.3 MPa of CO. II and III are active even in the absence of a base (TOF ca. 30 h(-1)). I is active only after addition of a base. A catalytic cycle is proposed. (C) 2013 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.11.009

文献信息

• Characterization and catalytic activity of trans-[Pd(COCH2CH3)(TsO)(PPh3)2], isolated from the hydro-methoxycarbonylation of ethene catalyzed by [Pd(TsO)2(PPh3)2]
  作者：Gianni Cavinato、Luigi Toniolo、Andrea Vavasori

  DOI：10.1016/j.molcata.2004.04.014

  日期：2004.9

  The title complex (I) has been isolated after running the hydro-methoxycarbonylation (HMC) of ethene (4.5 MPa Of CO/C2H4 = 1/1, 343 K) in MeOH, catalyzed by [Pd(TSO)(2)(PPh3)(2)]. It has been characterized by IR, H-1 and P-31 NMR spectroscopy.Complex (I) reacts with MeOH, saturated with CO, even at r.t., yielding methylpropanoate (NIP) in stoichiometric amount and Pd(0) complexes and/or trans- [Pd(COOCH3)(TsO)(PPh3)(2)] (II), the latter forms in the presence of PPh3 and of p-toluenesulfonic acid (TsOH); complex (I) catalyses the HMC of ethene to NIP; it catalyses also the HNIC of a different olefin yielding also a stoichiometric amount of MP. After catalysis. complex (I) is recovered as such or as [Pd(TSO)(2)(PPh3)(2)] (III), the latter forming when an excess of TsOH is used (Pd/TsOH = 1/8).Complex (II), a potential catalytic intermediate, has been prepared under conditions similar to those employed to synthesize complex (I), except for the presence of ethene. This complex, dissolved in MeOH saturated with C2H4, does not yield MP at r.t., whilst at 353 K, it becomes a catalyst precursor for the HMC of ethene, however, it is recovered as complex (I). The conversion of (II) to (I) occurs with CO2 evolution. For the conversion of (I) to (II), it is proposed that: (i) (I) reacts with MeOH yielding NIP and a Pd(II)-hydride; (ii) this reacts with TsOH with hydrogen evolution and yielding complex (III); (iii) this reacts with CO and MeOH yielding (II). For the conversion of (II) to (I) it is proposed that: (i) (II) reacts with H2O yielding MeOH and a Pd-COOH species; (ii) this evolves CO2 with formation of a Pd(II)-hydride; (iii) sequential addition of ethene and CO gives (I).In addition, it has also been found that catalysis is accompanied by formation of CO, also when using complex (I) as catalyst and that the catalytic activity passes through a maximum with increasing the concentration of water (TOF = 420 h(-1) at 353 K, 4.5 MPa CO/C2H4 = 1/1, (1)/PPh3/TsOH = 1/6/8t H2O = 800 ppm). It is proposed that: (i) catalysis occurs through initial formation of a Pd(II)-H species (which form after CO, evolution from a Pd-(COOH) species formed via interaction of H2O with CO), followed by the. insertion of the olefin into the Pd(H)-H bond to form a Pd(II)-(alkyl) intermediate, which in turn inserts CO with formation of an acyl complex of type (I), which reacts with MeOH yielding the ester and Pd(II)-H back to the catalytic cycle; (ii) a carbomethoxy complex of type (II) does not play a major direct role in the catalytic cycle; (iii) during the catalysis Pd(H)-H consuming side reactions occur with formation of Pd(II) species of type (II) and/or (III); these species are reintroduced, as hydrides, back to the catalytic cycle via interaction with H2O and CO. (C) 2004 Elsevier B.V. All rights reserved.
• An NMR study on the mechanism of ethene hydromethoxycarbonylation catalyzed by cationic Pd(II)–PPh3 complexes
  作者：E. Amadio、G. Cavinato、P. Härter、L. Toniolo

  DOI：10.1016/j.jorganchem.2013.07.043

  日期：2013.11

  The reactivity of cis-[Pd(H2O)(2)(PPh3)(2)](TsO)(2)center dot 2(H2O) (I,H2O), trans-[Pd(COEt)(TsO)(PPh3)(2)] (II) and trans[Pd(COOMe)(TsO)(PPh3)(2)] (III) has been studied by H-1 and P-31H-1} NMR spectroscopy under conditions that mime the catalytic ethene hydromethoxycarbonylation (EHMC), i.e. in the presence of PPh3, H2O and TsOH. (I,H2O), in the presence of two equivalents of PPh3, reacts with MeOH and CO (0.3 MPa) at 193 K to give [Pd(COOMe)(TsO)(PPh3)(3)] (III'), which reacts with H2O in the presence of TsOH at 293 K to generate [PdH(PPh3)(3)](TsO) (IV) quantitatively. This hydride inserts ethene (0.3 MPa, 293 K) to give trans[ Pd(Et)(TsO)(PPh3)(2)] (V), which reacts with CO (0.3 MPa, 223 K) giving [Pd(COEt)(PPh3)(3)](TsO) (II)' and initiates the catalytic EHMC at 293 K. II, in combination with PPh3 and TsOH, reacts at 293 K with MeOH with quantitative formation of methyl propanoate (MP) and IV and promotes the catalysis starting from this temperature, under 0.6 MPa of CO/ethene (1/1) when the ratio PPh3/TsOH/II is 2/6/1; upon increasing the PPh3/II ratio, the catalytic activity passes through a maximum when the ratio is 4/1, even though it initiates at a higher temperature. In the absence of added ligand, MP is formed in a stoichiometric amount, catalysis is not observed and decomposition to Pd metal occurs. Therefore, PPh3 is essential in order to stabilize hydride IV, though an excess of ligand is detrimental. III does not insert ethene even at 343 K, a temperature well above that at which catalysis is observed. All these experimental evidences support the Pd-H cycle. (C) 2013 Elsevier B. V. All rights reserved.