trans-bis(benzoato)bis(tricyclohexylphosphine)palladium(II) | 164019-42-5

• 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: trans-bis(benzoato)bis(tricyclohexylphosphine)palladium(II)
• CAS: 164019-42-5
• 化学式: C₅₀H₇₆O₄P₂Pd
• 分子量: 909.519
• InChiKey: HQGZUIMJLVJVJR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  15.55
• 重原子数：
  57.0
• 可旋转键数：
  12.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  lithium(etherate)2.5 tetrakis(pentafluorophenyl)borate 、 trans-bis(benzoato)bis(tricyclohexylphosphine)palladium(II) 在 p-toluenesulfonic acid monohydrate 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到(κ2-O,O'-benzoato)bis(tricyclohexylphosphine)palladium(II) tetrakis(pentafluorophenyl)borate
  参考文献：
  名称：

  带有路易斯碱的阳离子钯（II）膦羧酸盐配合物的反应性研究：取代与环金属化

  摘要：

  Two classes of cationic palladium(II) phosphine carboxylate complexes were isolated and characterized. Reactions of trans-[(R3P)(2)Pd(O2CR')(2)] (1) with [Li(OEt2)(2.5)][B(C6F5)(4)] in MeCN led to carboxylate abstraction and formation of trans-[(R3P)(2)Pd(O2CR')(MeCN)][B(C6F5)(4)] (2) in good to excellent yields. On the other hand, carboxylate abstraction reactions of 1 with [Me-2(H)NPh][B(C6F5)(4)] or p-toluenesulfonic acid (HOTs center dot H2O) in CH2Cl2 furnished the palladium cations [(R3P)(2)Pd(kappa(2)-O,O-O2CR')](+) (3). The reactions of 2 and 3 with Lewis bases were found to be different in some cases. For example, reactions of 2 with pyridine furnished the simple products of acetonitrile substitution, trans-[(R3P)(2)Pd(O2CR')(py)][B(C6F5)(4)]. In contrast, the reaction of 3e (R = Pr-i, R' = CH3) with CD3CN in the presence of excess sodium carbonate yielded a material derived from cyclometalation of one of the Pr-i arms of a (Pr3P)-Pr-i ligand. New complexes were characterized by elemental analyses and NMR (H-1, C-13, and P-31) spectroscopic methods and in two cases by single-crystal X-ray structural methods.

  DOI：

  10.1021/om070069g
• 作为产物：
  描述：

  palladium(II) benzoate 、 三环己基膦 以 二氯甲烷 为溶剂， 以74%的产率得到trans-bis(benzoato)bis(tricyclohexylphosphine)palladium(II)
  参考文献：
  名称：

  带有路易斯碱的阳离子钯（II）膦羧酸盐配合物的反应性研究：取代与环金属化

  摘要：

  Two classes of cationic palladium(II) phosphine carboxylate complexes were isolated and characterized. Reactions of trans-[(R3P)(2)Pd(O2CR')(2)] (1) with [Li(OEt2)(2.5)][B(C6F5)(4)] in MeCN led to carboxylate abstraction and formation of trans-[(R3P)(2)Pd(O2CR')(MeCN)][B(C6F5)(4)] (2) in good to excellent yields. On the other hand, carboxylate abstraction reactions of 1 with [Me-2(H)NPh][B(C6F5)(4)] or p-toluenesulfonic acid (HOTs center dot H2O) in CH2Cl2 furnished the palladium cations [(R3P)(2)Pd(kappa(2)-O,O-O2CR')](+) (3). The reactions of 2 and 3 with Lewis bases were found to be different in some cases. For example, reactions of 2 with pyridine furnished the simple products of acetonitrile substitution, trans-[(R3P)(2)Pd(O2CR')(py)][B(C6F5)(4)]. In contrast, the reaction of 3e (R = Pr-i, R' = CH3) with CD3CN in the presence of excess sodium carbonate yielded a material derived from cyclometalation of one of the Pr-i arms of a (Pr3P)-Pr-i ligand. New complexes were characterized by elemental analyses and NMR (H-1, C-13, and P-31) spectroscopic methods and in two cases by single-crystal X-ray structural methods.

  DOI：

  10.1021/om070069g

文献信息

• Single component cationic palladium proinitiators for the latent polymerization of cycloolefins
  申请人：Bell Andrew

  公开号：US20050187398A1

  公开（公告）日：2005-08-25

  Palladium compound compositions are provided in accordance with Formulae [((R) 3 E) a Pd(Q)(LB) b ] p [WCA] r , where ((R) 3 E) is a Group 15 electron donor ligand, Q is an anionic ligand, LB is a Lewis base, WCA is a weakly coordinating anion, a is 1, 2 or 3, b is 0, 1 or 2, the sum of a and b is 1, 2 or 3 and each of p and r is an integer such that the molecular charge is zero, or [(E(R) 3 )(E(R) 2 R*)Pd(LB)] p [WCA] r where E(R) 2 R* represents a Group 15 neutral electron donor ligand and where R* is an anionic hydrocarbyl containing moiety, bonded to the Pd and having a β hydrogen with respect to the Pd center. Such compound composition exhibits latent polymerization activity in the presence of polycyclic olefins.

  钯化合物组成按照以下公式提供：[((R)3E)aPd(Q)(LB)b]p[WCA]r，其中((R)3E)是第15族电子供体配体，Q是阴离子配体，LB是路易斯碱，WCA是弱配位阴离子，a为1、2或3，b为0、1或2，a和b的总和为1、2或3，p和r各自为整数，使得分子电荷为零，或[(E(R)3)(E(R)2R*)Pd(LB)]p[WCA]r，其中E(R)2R*代表第15族中性电子供体配体，R*是与Pd键合的含有阴离子烃基的部分，并且相对于Pd中心具有β氢。这种化合物组成在多环烯烃存在时表现出潜在的聚合活性。
• Indirect Formation of Carboxylic Acids via Anhydrides in the Palladium-Catalyzed Hydroxycarbonylation of Aromatic Halides
  作者：Vladimir V. Grushin、Howard Alper

  DOI：10.1021/ja00120a012

  日期：1995.4

  The carbonylation of [(Ph(3)P)(2)Pd(2)Ph(2)(mu-OH)(2)] (2) in the presence of PhI results in the quantitative formation of benzoic anhydride and [(Ph(3)P)(2)Pd-2(PhCO)(2)(mu-I)(2)] (3). This transformation contributes to some extent to the production of benzoic acid from haloarenes, CO, and alkali, catalyzed by [(Ph(3)P)(2)PdCl2], the latter being converted to 2 under the reaction conditions. Phenyl- and benzoylpalladium benzoates are likely key intermediates in the indirect formation of the acid, via the anhydride, by the carbonylation of 2. One such complex, [L(2)Pd(Ph)(PhCOO)] (5, L Cy(3)P), was isolated from the carbonylation of [(Cy(3)P)(2)Pd(2)Ph(2)(mu-OH)(2)] (4) in hexane. The related complexes, [L(2)Pd(2)Ph(2)(mu-PhCOO)(2)] (6, L = PPh(3); 7, L = PCy(3)), were prepared from benzoic acid and hydroxo complexes 2 and 4, respectively. Treatment of 6 and 7 with the corresponding phosphine afforded [L(2)pd(ph)(phCOO)] (8, L = PPh(3); 5, L = PCy(3)). When 6-8 were reacted with CO in benzene, benzoic anhydride was readily formed, whereas in the case of 5 both carbonylation and reductive elimination were sluggish. Crystallographic data for 6 (1:2 chloroform solvate): space group Peen, a = 22.499(4) Angstrom, b = 10.992(3) Angstrom, c = 24.514(6) Angstrom, V = 6062.4(23) Angstrom(3), Z = 4, R = 0.056, and R(w) = 0.038.