tetrakis(tris(4-methyl)phenyl)phosphinepalladium | 29032-56-2

• 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: tetrakis(tris(4-methyl)phenyl)phosphinepalladium
• 英文别名: tetrakis(tri-p-tolylphosphine) palladium；Pd[P(4-CH3-Ph)3]4；Pd(P(p-Tol)3)4；palladium;tris(4-methylphenyl)phosphane
• CAS: 29032-56-2
• 化学式: C₈₄H₈₄P₄Pd
• 分子量: 1323.91
• InChiKey: CROMVTSWACNGDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.48
• 重原子数：
  89.0
• 可旋转键数：
  16.0
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  tetrakis(tris(4-methyl)phenyl)phosphinepalladium 、 苯甲酰氯 以94%的产率得到trans-Pd{P(p-tolyl)3}2(Cl)(COPh)
  参考文献：
  名称：

  钯 (II) 配合物中酰基异构化的机制。羧酸氯化物异构化催化工艺的开发

  摘要：

  Le complexe cationique [Pd(PPh 3 ) 2 (MeCN)(COiPr)](BF 4 ) s'isomerise en solution spontanement en complexe [Pd(PPh 3 ) 2 (MeCN)(CoPr)](BF 4 ), on obtient ainsi un melange des deux complexes. Plusieurs 举例说明了 d' 异构化及其复合物 [Pd(PPh 3 ) 2 (MeCN)(COR)](BF 4 ) ou R=Bu/sec-Bu、i-Bu/t-Bu 和甲基环己基。En 存在 d'un 超过 d' 乙烯 ou de cyclohexene une 反应 d'echange donne complexe avec R = 乙基和 R = 环己基。Enfin, l'isomerisation catalytique

  DOI：

  10.1021/ja00211a020
• 作为产物：
  描述：

  、 在 t-BuOK-d9 作用下， 以 氘代四氢呋喃 为溶剂， 生成 、 tetrakis(tris(4-methyl)phenyl)phosphinepalladium 、 3,3-dimethyl-1-(triphenylphosphanylidene)butan-2-one
  参考文献：
  名称：

  瞬态钯（0）亚烷基的合成与检测方法

  摘要：

  DOI：

  10.1021/om00132a022
• 作为试剂：
  描述：

  ((2R,3S,6S)-3-acetoxy-6-cyano-3,6-dihydro-2H-pyran-2-yl)methyl acetate 在 tetrakis(tris(4-methyl)phenyl)phosphinepalladium 、 二苯基硅烷 、 zinc(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 [(2S,6S)-6-cyano-3,6-dihydro-2H-pyran-2-yl]methyl acetate 、 [(2S,6S)-2-cyano-3,6-dihydro-2H-pyran-6-yl]methyl acetate
  参考文献：
  名称：

  Selective deoxygenation of unsaturated carbohydrates with Pd(0)/Ph2SiH2/ZnCl2. Total synthesis of (+)-(S,S)-(6-methyltetrahydropyran-2-yl)acetic acid

  摘要：

  DOI：

  10.1021/jo00251a011

文献信息

• Synthesis and reactivity of phenoxycarbonyl palladium complex: relevant to the mechanism of oxidative carbonylation of phenol
  作者：Hiroyuki Yasuda、Noriko Maki、Jun-Chul Choi、Toshiyasu Sakakura

  DOI：10.1016/s0022-328x(03)00696-x

  日期：2003.10

  Phenoxycarbonyl palladium complex was synthesized and its reactivity was investigated relevant to the mechanism of the palladium-catalyzed oxidative carbonylation of phenol to produce diphenyl carbonate (DPC). The phenoxycarbonyl palladium complex PdCl(CO2Ph)(PPh3)2 (1) was synthesized by oxidative addition of phenyl chloroformate to Pd(PPh3)4. Complex 1 could be isolated as single crystals and characterized

  合成了苯氧羰基钯配合物，并研究了其反应性与钯催化苯酚氧化羰基化生成碳酸二苯酯（DPC）的机理有关。苯氧羰基钯配合物PdCl（CO 2 Ph）（PPh 3）2（1）是通过将氯甲酸苯酯氧化添加到Pd（PPh 3）4中而合成的。可以将复合物1分离为单晶并通过X射线晶体学表征。1的热分解导致DPC的形成，尽管同时发生了PPh 3配体向PhCl和PhCO 2 Ph的降解。氯化钯2（PPh 3）2是主要的新形成的钯物质。对于1与氯甲酸苯酯的反应，观察到有效的DPC形成。另一方面，1与苯酚钠（一个当量）的反应在-20°C进行，导致立即形成了可分配给Pd（OPh）（CO 2 Ph）（PPh 3）2（2）的新物质。由NMR（1 H，13 C 1 H}和31 P 1H}）光谱；酚盐的亲核攻击优先发生在钯中心而不是羰基上。加热反应混合物时，可能通过从2中的还原消除反应生成了DPC 。这些结果以及先前的发
• 1,3-Diphosphorus Ylide Cyclopentadienylium Salts: Synthesis, Structures, and Application in Coupling Reactions
  作者：Chen Xu、Zhi-Qiang Wang、Zhen Li、Wei-Zhou Wang、Xin-Qi Hao、Wei-Jun Fu、Jun-Fang Gong、Bao-Ming Ji、Mao-Ping Song

  DOI：10.1021/om201267q

  日期：2012.2.13

  The 1,3-diphosphorus ylide cyclopentadienylium salts (C5H3)(PPh3)2I (1) and (C5H3)[P(4-CH3-Ph)3]2I (2) have been prepared from the reaction of 1,1′-dichloromercurioferrocene with Pd(PPh3)4 and with Pd[P(4-CH3-Ph)3]4, respectively. The molecular structure of 1 has been determined by X-ray diffraction analyses. The Pd(OAc)2/1 or 2/KtOBu system is highly efficient for the coupling reactions of aryl chlorides

  1,3-二磷内酯环戊二烯鎓盐（C 5 H 3）（PPh 3）2 I（1）和（C 5 H 3）[P（4-CH 3 -Ph）3 ] 2 I（2）已分别由1,1'-二氯汞二茂铁与Pd（PPh 3）4和Pd [P（4-CH 3 -Ph）3 ] 4反应制得。的分子结构1已经通过X射线衍射分析来确定。将Pd（OAc）2 / 1或2/ K t OBu系统对于室温下芳基氯的偶联反应非常有效。
• Synthesis and Structure of η²-Phosphonioalkene−Palladium(0) Complexes. A Catalyst Intermediate in the Palladium-Mediated Synthesis of Alkenylphosphonium Halides
  作者：Chien-Chih Huang、Jiun-Pey Duan、Ming-Yuan Wu、Fen-Ling Liao、Sue-Lein Wang、Chien-Hong Cheng

  DOI：10.1021/om970709n

  日期：1998.2.1

  Treatment of Pd(PPh3)(4) with PhCH=CHBr in THF at 45 degrees C gave [(trans-PhCH=CHPPh3)Pd(PPh3)(2)]Br-+(-) (1), which was found to be converted from Pd(PPh3)(2)(CH=CHPh)Br. X-ray structural analysis shows that 1 adopts a distorted-square-planar geometry with two PPh3 ligands and a (PhCH=CHPPh3)(+) moiety. The C-C double bond in the latter is pi-bonded to the palladium(0) center and occupies two of the four square-planar coordination sites. Under similar reaction conditions, Pd[P-trans-PhCH=CHP(p-tolyl)(3)][P(p-tolyl)(3)](2)}Br-+(-) (2) was formed from Pd[P(p-tolyl)(3)](4) and PhCH=CHBr, while [(trans-MeCH=CHPPh3)Pd(PPh3)(2)]Br-+(-) (3) was isolated from the reactions of Pd(PPh3)4 with MeCH=CHBr. Treating PhCH=CHBr with trans-Pd(PPh3)(2)(C6H4O-p-CH3)I in THF at ambient temperature led to the formation of (trans-PhCH=CHPPh3)Pd(PPh3)X (5) and (p-CH3OC6H4PPh3)X-+(-) (X, mixture of Br and I). Complex 5 (X Br) can be prepared by treating trans-PhCH=CH(PPh3)Br-+(-) with Pd(dba)(2) and 1 equiv of PPh3 in CH2Cl2. X-ray analysis shows 5 adopts a distorted-square-planar structure consisting of PPh3, X, and PhCH=CH(PPh3)(+) as ligands. The PPh3 ligand is trans to the olefin carbon that is connected to the PPh3 group in PhCH=CH(PPh3)(+), while the halide ligand is trans to the olefin carbon bonded to a phenyl moiety. Reaction of 5 (X = Br) with 1 equiv of PPh3 at ambient temperature afforded 1 in high yield. Pd(PPh3)(4) or Pd(OAc)(2) catalyzes the reactions of PPh3 with PhCH=CHBr, MeCH=CHBr, MeCH=C(Me)Br (mixtures of isomers), CH2=C(Me)Br, cis-(EtO2C)CH=CHBr, and cis-(MeO2C)CH=CHBr to give the corresponding trans-RCH=CR'(PPh3)Br-+(-). During the reaction of PPh3 with PhCH-CHBr, 1 was found to be a catalyst intermediate in the reaction solution. All the pho sphonioalkene-palladium(0) complexes and alkenylphosphonium halides isolated are trans in the (RCH-CR'PPh3)(+) moiety.
• Insertion of olefins into palladium(II)-acyl bonds. Mechanistic and structural studies
  作者：Jeffrey S. Brumbaugh、Robert R. Whittle、Masood Parvez、Ayusman Sen

  DOI：10.1021/om00156a010

  日期：1990.6