dichlorobis(trimethylphosphite)palladium(II) | 30153-54-9

• 分子结构分类: 有机化合物 - 有机磷化合物 - 亚磷酸三烷基酯
• 英文名称: dichlorobis(trimethylphosphite)palladium(II)
• 英文别名: Palladium(2+);trimethyl phosphite;dichloride；palladium(2+);trimethyl phosphite;dichloride
• CAS: 30153-54-9；17787-26-7
• 化学式: C₆H₁₈Cl₂O₆P₂Pd
• 分子量: 425.479
• InChiKey: GUVFHQCTHVUHGO-UHFFFAOYSA-L

物化性质

• 沸点：
  173-174 °C(lit.)
• 密度：
  1.4850 g/mL at 25 °C(lit.)
• 闪点：
  154 °F

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dichlorobis(trimethylphosphite)palladium(II) 、 2-((diphenylphosphino)amido)pyridine 以 二氯甲烷 为溶剂， 以95%的产率得到cis-[PdCl(2-(diphenylphosphinoamino)pyridine-P,N)(P(OMe)3)]Cl
  参考文献：
  名称：

  The co-ordination chemistry of 2-(diphenylphosphinoamino)pyridine †

  摘要：

  2-(二苯膦氨基)吡啶，dppap [Ph2PNHpy]，以及超过40个示例性的其配合物已被制备。在一系列钯、铂和金配合物中，示例了中性（以及双齿去质子化配体）的单齿、双齿和桥联配位方式。十个示范性例子通过单晶X射线衍射进行了表征。Ph2PNHpy以氢键结合的二聚体对形式存在；cis-[PtCl(Ph2PNHpy-P,N){Ph2PNHpy-P}]Cl通过氢键形成无限链；cis-[Pt(Ph2PNpy-P,N)2]和cis-[Pd(Ph2PNpy-P,N)2]是同构的。cis-[Pd(Ph2PNHpy-P,N)2][BF4]2、[AuCl(Ph2PNHpy-P)]、[Pt(C8H12OMe)(Ph2PNpy-P,N)]·H2O展示了氢键结合，cis-[PtCl(Ph2PNHpy-P,N)(PMe3)]Cl、cis-[PtCl(Ph2PNpy-P,N)(PMe3)]和cis-[PtCl(Ph2PNHpy-P,N)(P(OPh)3)]Cl的结构也被报道。

  DOI：

  10.1039/b003294h
• 作为产物：
  描述：

  甲醇 、 dichlorobis(phosphorustrichloride)palladium (II) 生成 dichlorobis(trimethylphosphite)palladium(II)
  参考文献：
  名称：

  Fink, E., Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1896, vol. 123, p. 603 - 603

  摘要：

  DOI：
• 作为试剂：
  描述：

  二苯基乙炔 、 反式-2-苯乙烯硼酸频哪酸酯 在 copper diacetate 、 dichlorobis(trimethylphosphite)palladium(II) 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以81%的产率得到1,2,3,4,6-pentaphenylfulvene
  参考文献：
  名称：

  Mizoroki−Heck Type Reaction of Organoboron Reagents with Alkenes and Alkynes. A Pd(II)-Catalyzed Pathway with Cu(OAc)₂ as an Oxidant

  摘要：

  [GRAPHICS]In contrast to the Pd(0)-catalyzed mechanism by Uemura, Mizoroki-Heck type reaction of boronic acids is found to proceed under a Pd(ll)mediated pathway using a catalytic amount of Pd(OAc)(2) in the presence of Cu(OAc)(2) as an oxidant. Treatment of a variety of alkenes with boronic acids, boronates, and sodium tetraphenylborate furnishes beta -arylated and alkenylated products in good to excellent yields. The reactions with norbornene, norbornadiene, and diphenylacetylene are also performed to give 1:2 or 2:1 coupling products.

  DOI：

  10.1021/ol016529y

文献信息

• Structural studies of PdCl₂L₂ complexes with fluorinated phosphines, phosphites, and phosphinites as precursors of benzyl bromide carbonylation catalysts, and and X-ray crystal structure of <i>cis</i>-PdCl₂[PPh₂(OEt)]₂
  作者：Anna M Trzeciak、Hubert Bartosz-Bechowski、Zbigniew Ciunik、Katarzyna Niesyty、Józef J Ziólkowski

  DOI：10.1139/v01-075

  日期：2001.5.1

  PdCl₂L₂-type complexes with phosphines (L = PPh_x(C₆F₅)_3-x (x = 0-3)), phosphites (L = P(OMe)₃, P(OPh)₃, P(OEt)₃), and phosphinites (L = PPh₂(OC₆F₅), PPh₂(O-3,5-F₂C₆H₃), PPh₂(OEt), PPh₂(O-n-Bu), PPh₂(O-t-Bu)) were synthesized and characterized by UV-vis and ³¹P NMR methods. PdCl₂L₂ complexes with less sterically demanding phosphines (Θ < 140°) exist as cis isomers, which is confirmed by the X-ray structure of cis-PdCl₂[PPh₂(OEt)]₂. These complexes react with CO in the presence of NEt₃ forming Pd(CO)_xL_y (x + y = 4) type carbonyls characterized by IR spectra. All PdCl₂L₂ complexes studied are active as precursors of benzyl bromide carbonylation catalysts at 40°C and 1 atm CO; however, the activity of the cis isomers is higher than that of the trans isomers. The highest yields of the carbonylation product, phenylacetic acid methyl ester, were obtained using cis-PdCl₂[P(OMe)₃]₂ (92%), cis-PdCl₂[P(OPh)₃]₂ (89%), and cis-PdCl₂[PPh₂(O-n-Bu)]₂ (78%) as catalyst precursors.Key words: palladium complexes, fluorinated phosphines, benzyl bromide carbonylation.

  PdCl₂L₂型配合物与膦配体（L = PPhₓ(C₆F₅)₃⁻ₓ (x = 0-3)）、膦酸酯（L = P(OMe)₃, P(OPh)₃, P(OEt)₃）和膦酰胺（L = PPh₂(OC₆F₅), PPh₂(O-3,5-F₂C₆H₃), PPh₂(OEt), PPh₂(O-n-Bu), PPh₂(O-t-Bu)）被合成并通过UV-vis和31P NMR方法进行表征。较少空间位阻的膦配体（Θ < 140°）形成的PdCl₂L₂配合物存在顺式异构体，这通过顺式-PdCl₂[PPh₂(OEt)]₂的X射线结构得到证实。这些配合物在NEt₃存在下与CO反应形成Pd(CO)ₓLᵧ（x + y = 4）类型的羰基化合物，其特征是IR光谱。所有研究的PdCl₂L₂配合物在40°C和1大气压CO下作为苄溴羰基化催化剂的前体具有活性；然而，顺式异构体的活性高于反式异构体。通过使用顺式-PdCl₂[P(OMe)₃]₂（92%）、顺式-PdCl₂[P(OPh)₃]₂（89%）和顺式-PdCl₂[PPh₂(O-n-Bu)]₂（78%）作为催化剂前体，可以获得苄溴羰基化产物苯乙酸甲酯的最高收率。关键词：钯配合物，氟代膦，苄溴羰基化。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Pd: MVol.2, 128, page 412 - 415
  作者：

  DOI：——

  日期：——
• The influence of steric bulk on the geometry of triarylphosphite-based palladacycles and their tricyclohexylphosphine adducts
  作者：Robin B. Bedford、Michael Betham、Simon J. Coles、Peter N. Horton、María-José López-Sáez

  DOI：10.1016/j.poly.2005.11.014

  日期：2006.3

  A range of complexes of the formula [PdCl2P(OAr)(3)}(2)] have been synthesized in order to determine the effect of steric bulk on stereochemistry, one example [PdCl2P(OC6H4-2-Bu-t)(3)}(2)] has been structurally characterized. Three palladacyclic complexes [Pd(mu-Cl)-(kappa(2)-P, C-P(OC6H3R)(OC6H4R)(2))}(2)] have been synthesized (R = H, 2-Pr-t, 2-Bu-t) and two have been characterized by crystallography (R = H and Bu-t). The latter adopts the expected trans geometry while the former is cis. In this case, the driving force for the cis geometry seems to be intermolecular interactions in the crystal structure which are disrupted on substitution. We also report an unusual solvolysis reaction. (c) 2005 Elsevier Ltd. All rights reserved.
• Fink, E., Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1896, vol. 123, p. 604 - 604
  作者：Fink, E.

  DOI：——

  日期：——
• Fink, E., Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1896, vol. 123, p. 603 - 603
  作者：Fink, E.

  DOI：——

  日期：——