allylpalladium(triisopropylphosphine) chloride | 244159-79-3

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: allylpalladium(triisopropylphosphine) chloride
• 英文别名: [Pd(allyl)(triisopropylphosphine)Cl]；[(η³-allyl)Pd(P(ⁱPr)₃)(Cl)]；(iPr3P)Pd(η3-C3H5)Cl；Palladium(2+);prop-1-ene;tri(propan-2-yl)phosphane;chloride；palladium(2+);prop-1-ene;tri(propan-2-yl)phosphane;chloride
• CAS: 244159-79-3
• 化学式: C₁₂H₂₆ClPPd
• 分子量: 343.185
• InChiKey: OBBRVDXULMHDMF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  thallium tetrakis(pentafluorophenyl)borate 、 allylpalladium(triisopropylphosphine) chloride 以 二氯甲烷 为溶剂， 以52%的产率得到[((η3-allyl)Pd(P-i-Pr3))2(μ-Cl)][B(C6F5)4]
  参考文献：
  名称：

  双核[{（π-C 3 H ^ 5）M（PR 3）} 2（μ-X）]镍和钯Y的配合物†

  摘要：

  双卤化物桥连的π烯丙基络合物{（η 3 -C 3 H ^ 5）M（μ-X）} 2（M =镍，钯; X =氯，溴）的弱配位阴离子的盐铊卤化物抗蚀抽象在非配位CH 2 Cl 2中，Y ＝ PF 6，B（C 6 F 5）4和B {C 6 H 3（CF 3）2 } 4。在大体积的膦的存在下（P我镨3，P吨卜3），或者当2当量的（η 3 -C 3ħ 5）M（PR 3）X与TLY，卤化物离子中的一个被替换，以得到离子的双核反应，单卤化物桥连的络合物[{（η 3 -C 3 H ^ 5）M（PR 3）} 2（μ-X）] Y（M =镍，X = Br的（6，7）; M =钯，X =氯（8，9）和Br（10，11）），其不与进一步TLY反应。Y = Al {OC（CF 3）3 } 4的相应配合物也已经准备好了。另外，已经发现，对于Y ＝ OTf，双核钯络合物而不是镍衍生物也是稳定的。根据NMR，该络合物代表溶液中非对映异构体的混合物。对于[{（η

  DOI：

  10.1021/om050020f
• 作为产物：
  描述：

  bis(η3-allyl-μ-chloropalladium(II)) 、 三异丙基膦 以 甲苯 为溶剂， 反应 48.0h， 以5.7 g的产率得到allylpalladium(triisopropylphosphine) chloride
  参考文献：
  名称：

  ORGANOPALLADIUM COMPOUNDS AS POLYMERIZATION CATALYSTS

  摘要：

  公开了一系列具有作为加成聚合催化剂的用途的双环烯基钯化合物。还公开了制备这些化合物的方法。

  公开号：

  US20160046657A1

文献信息

• Development, Synthetic Scope, and Mechanistic Studies of the Palladium-Catalyzed Cycloisomerization of Functionalized 1,6-Dienes in the Presence of Silane
  作者：Philip Kisanga、Ross A. Widenhoefer

  DOI：10.1021/ja001730+

  日期：2000.10.1

  A 1:1 mixture of the pi-allyl palladium complex (eta (3)-C3H5)Pd(CI)PCy3 Cia) and NaB[3,5-C6H3(CF3)(2)](4) in the presence of HSiEt3 catalyzed the cycloisomerization of diethyl diallylmalonate (2b) to form 4,4-dicarbomethoxy 1,2-dimethylcyclopentane (3b) in 98% yield with 98% isomeric purity. The procedure tolerated a range of functionality including esters, ketones, sulfones, protected alcohols, and substitution at the allylic and terminal olefinic carbon atoms. Cycloisomerization of 2b obeyed zero-order kinetics to >3 half-lives with initial formation of 1,1-dicarboethoxy-4-methyl-3-methylenecyclopentane (4b), followed by secondary isomerization to 3b. Deuterium labeling studies revealed that the conversion of 2b to 4b was accompanied by significant H/D exchange, consistent with an addition/elimination pathway coupled with facile H/D exchange of the Pd-H(D) intermediates with free silane.
• A Dinuclear Palladium(I) Ethynyl Complex:  Synthesis, Structure, and Dynamics
  作者：Jochen Krause、Richard Goddard、Richard Mynott、Klaus-Richard Pörschke

  DOI：10.1021/om000765f

  日期：2001.5.1

  The reaction of Pd(eta (3)-C3H5)(2) with (PPr3)-Pr-i at -30 degreesC affords yellow crystals of the Pd-II complex ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)(eta (3)-C3H5) (1). At 20 degreesC 1 transforms into the dinuclear Pd-I complex ((Pr3P)-Pr-i)Pd)(2)(mu -C3H5)(2) (2) due to oxidative C-C coupling of two allyl groups with elimination of 1,5-hexadiene. Heating 1 or 2 in 1,6-heptadiene to 80 degreesC produces the Pd-0 complex ((Pr3P)-Pr-i)Pd(eta (2),eta (2)-C7H12) (3) (eta (3)-C3H5)PdCl}(2) reacts with (Pr3P)-Pr-i to give ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)Cl (4b), from which further derivatives ((Pr3P)-Pr-i)Pd(eta (3)-C3H5)X (X = OSO2CF3 (4a), C drop CH (5a), CH3 (5b)) are obtained by replacement reactions. The mononuclear Pd-II-acetylide Sa and complex 3 combine to give the dinuclear Pd-I derivative ((Pr3P)-Pr-i)Pd}(2)(mu -C3H5)(mu (2)-eta (2)-C2H) (6). The Pd-Pd bond in 6 is unsymmetrically bridged by a pi -allyl and a sigma-pi -ethynyl group, as determined by X-ray structure analysis. The structures of 1, 4a,b, and 6 are dynamic in solution, with 1 undergoing an exchange of the binding modes of the pi- and sigma -coordinated allyl groups and 4a,b displaying a pi/sigma -allyl group rearrangement, and in 6 the C drop CH substituent oscillates in its pi -coordination from one Pd-I atom to the other.