cis-[PdCl₂(CN(t-Bu))₂] | 34710-33-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: cis-[PdCl₂(CN(t-Bu))₂]
• 英文别名: Dichloropalladium;2-isocyano-2-methylpropane
• CAS: 34710-33-3
• 化学式: C₁₀H₁₈Cl₂N₂Pd
• 分子量: 343.592
• InChiKey: IAEOWCDGISANMK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.78
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  8.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-[PdCl₂(CN(t-Bu))₂] 、 3,3-bis(dimethylphenylphosphine)-1,2-diarsa-3-palladium-closo-dodecaborane 以 四氢呋喃 为溶剂， 以28.3%的产率得到1-(t)BuNC-5-CN-1-(PMe2Ph)-closo-1,2,3-PdAs2B9H8
  参考文献：
  名称：

  Palladium-Assisted Cyano Substitution Reactions of (PMe2Ph)2Pd(B9H9As2) and (PMe2Ph)2Pd(B9C2H11). X-ray Crystal and Molecular Structures of 5-CN-1,1-(PMe2Ph)2-closo-1,2,3-PdAs2B9H8, 1-tBuNC-5-CN-1-(PMe2Ph)-closo-1,2,3-PdAs2B9H8, and 4,5-(CN)2-1,1-(PMe2Ph)2-closo-1,2,3-PdC2B9H9

  摘要：

  The reaction of 1,1-(PMe(2)Ph)(2)-closo-1,2,3-PdAs2B9H9 (A) with (1)BuNC formed low yields of 5-CN-1,1-(PMe(2)-Ph)(2)-closo-1,2,3-PdAs2B9K8 (2) and/or 1-(t)BuNC-5-CN-1-(PMe(2)Ph)-closo-1,2,3-PdAs2B9H8 (3). The use of ((t)BuNC)(2)PdCl2 as a reagent in this reaction gave an improved yield of compound 3. Similar reaction of 1,1-(PMe(2)Ph)(2)-closo-1,2,3-PdC2B9H11 (4) with ((t)BuNC)(2)PdCl2 gave 4.5-(CN)(2)-1,1-(PMe(2)Ph)(2)-closo-1,2,3-PdC2B9H9 (5). Reaction of A with (PMe(2)Ph)(2)P(CN)(2) gave 1-CN-1,5-(PMe(2)Ph)(2)-closo-1,2,3-PdAs2B9H8 (1) in low yield. Compounds 2, 3, and 5 were characterized by X-ray diffraction studies. Compound 2 consisted of bright purple crystals of monoclinic space group P2(1)/n, with a = 12.460(2) Angstrom, b = 11.583(2) Angstrom, c = 19.114(4) Angstrom, beta = 107.31(1)degrees, and Z = 4. The structure was determined by conventional heavy-atom methods and refined to a final value of R = 0.0432 (3899 reflections) and R(w) = 0.0458. Compound 3 consisted of magenta plates with triclinic space group , with a = 11.586(3) Angstrom, b = 11.813(3) Angstrom, c = 9.799(2) Angstrom, alpha = 95.33(1)degrees, beta = 114.58(1)degrees, gamma = 80.17(1)degrees, and Z = 2. The structure was determined by conventional heavy-atom methods and refined to a final value of R = 0.0235 (3323 reflections), R(w) = 0.0245. Compound 5 consisted of red needles with monoclinic space group P2(1)/n, with a = 10.383(2) Angstrom, b = 18.875(3) Angstrom, c = 13.682(2) Angstrom, beta = 105.41(1)degrees, and Z = 4. The structure was determined by conventional heavy-atom methods and refined to a final value of R = 0.0362 (3547 reflections), R(w) = 0.0335.

  DOI：

  10.1021/ic00130a007
• 作为产物：
  描述：

  {Pd(t-BuNC)2Cl}2*C6H5Cl 以 further solvent(s) 为溶剂， 生成 cis-[PdCl₂(CN(t-Bu))₂]
  参考文献：
  名称：

  钯盐催化：XIII。以Pd II和Pd 0配合物为均相催化剂将硝基芳族化合物还原羰基化为异氰酸酯

  摘要：

  在[Pd（异喹啉）2 ]存在下，通过催化作用将2,4-二硝基甲苯（2,4-DNT）还原羰基化为2,4-二异氰基甲苯（2,4-TDI）的研究。 Fe 2 O 3和MoO 3或Fe 2（MoO 4）3作为助催化剂，或由不含助催化剂的Pd o配合物组成。在基于[Pd（异喹啉）2 Cl 2 ]的催化体系的情况下，该反应可以在约200℃和200atm的CO下进行以产生具有高转化率和可接受的选择性的2，4-TDI。Pd 0配合物作为催化剂可以在低得多的温度下（100-120°C）达到良好的转化率，但是当使用较高的CO压力（300 atm或更高）时选择性低。对硝基苯还原羰基化为苯基异氰酸酯作为模型系统的研究，以及对在CO存在下[Pd（异喹啉）2 Cl 2 ]的热稳定性的研究，提供了证据，表明实际的活性催化剂可能是一种硝基芳族底物或由其作为配体形成的一些产品稳定化后的钯还原形式（可能为零价）。

  DOI：

  10.1016/0022-328x(91)80175-j
• 作为试剂：
  描述：

  碘苯 、 1-甲氧基-4-(3,3,3-三氟丙-1-炔基)苯 在 cis-[PdCl₂(CN(t-Bu))₂] 、 六正丁基二锡 、 copper(l) iodide 、 四(三苯基膦)钯 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 (Z)-1-(4-methoxyphenyl)-1,2-diphenyl-3,3,3-trifluoropropene
  参考文献：
  名称：

  An Efficient Protocol for the Stereoselective Construction of Multisubstituted Fluorine-Containing Alkenes. A Palladium-Catalyzed Bisstannylation of Fluorinated Internal Alkynes

  摘要：

  On treatment of various fluorinated internal alkynes with 1.2 equiv of hexabutylditin under the influence of 2.5 mol % of Pd(t-BuNC)(2)Cl(2) in THF at room temperature for 4 h, the bisstannylation proceeded smoothly to afford the corresponding bisstannylaled cis-adducts in high yields. Thus obtained adducts were subjected to the Stille cross-coupling reaction to give the corresponding tetrasubstituted fluorine-containing alkenes with defined stereochemistry in good yields.

  DOI：

  10.1021/jo9017028

文献信息

• Syntheses and Structures of a Series of Acyclic Diaminocarbene Palladium(II) Complexes Derived from 3,4-Diaryl-1<i>H</i>-pyrrol-2,5-diimines and Bisisocyanide Palladium(II) Complexes
  作者：Dina V. Boyarskaya、Evgeny Bulatov、Irina A. Boyarskaya、Tatiana G. Chulkova、Valentin A. Rassadin、Elena G. Tolstopjatova、Ilya E. Kolesnikov、Margarita S. Avdontceva、Taras L. Panikorovskii、Vitalii V. Suslonov、Matti Haukka

  DOI：10.1021/acs.organomet.8b00725

  日期：2019.1.28

  2-sulfonyloxyphenyl), one isocyanide ligand is displaced from the coordination sphere. Structural features of the prepared diaminocarbene complexes have been studied by molecular spectroscopy techniques, cyclic voltammetry, single-crystal X-ray diffraction, and DFT calculations. The photophysical properties of the obtained acyclic diaminocarbene complexes in solution mainly depend on the substituents in the

  研究了3,4-二芳基-1 H-吡咯-2,5-二亚胺与各种双异氰化物钯（II）配合物的反应。与一个异氰化物配体进行偶联以完成无环二氨基卡宾配合物。生成的二氨基卡宾配合物的结构取决于钯（II）的双异氰化物配合物中异氰化物配体的体积。亚氨基的基团的3,4-二芳基-1- ħ与一种异氰化物配体-吡咯烷-2,5-二亚胺起反应的顺式- [的PdCl 2（CN-R）2 ]（R =我-Pr中，Cy，吨- Bu，Bn），并且吡咯环的氮原子与钯中心配位，因为第二异氰酸酯配体保持完整。如果是顺式-[PdCl 2（CN–R）2 ]（R = 2-酰氧基苯基，2-磺酰氧基苯基），一个异氰化物配体从配位球中置换出来。已通过分子光谱技术，循环伏安法，单晶X射线衍射和DFT计算研究了制备的二氨基卡宾配合物的结构特征。溶液中获得的无环二氨基卡宾配合物的光物理性质主要取决于3，4-二芳基-1 H-吡咯-2，5-二亚胺部分中的取代基。
• Chemoselective Pd-Catalyzed Isocyanide Insertion Reaction of Enaminones by C-H Functionalization: Hydrolysis or Cyclization through 1,3-Palladium Migration
  作者：Zheng-Yang Gu、Xiang Wang、Jia-Jia Cao、Shun-Yi Wang、Shun-Jun Ji

  DOI：10.1002/ejoc.201500458

  日期：2015.7

  A chemoselective palladium-catalyzed isocyanide insertion reaction of enaminones was developed. Amide derivatives were synthesized by this C–H functionalization and subsequent hydrolysis reactions. 4-Aminoquinoline derivatives were prepared by this C–H functionalization, which includes a 1,3-palladium migration in the process.

  开发了一种化学选择性钯催化的烯胺酮异氰化物插入反应。通过这种 C-H 官能化和随后的水解反应合成酰胺衍生物。4-氨基喹啉衍生物是通过这种 C-H 官能化制备的，其中包括在该过程中的 1,3-钯迁移。
• Novel Palladium–Aminocarbene Species Derived from Metal-Mediated Coupling of Isonitriles and 1,3-Diiminoisoindoline: Synthesis and Catalytic Application in Suzuki–Miyaura Cross-Coupling
  作者：Rogério S. Chay、Konstantin V. Luzyanin、Vadim Yu. Kukushkin、M. Fátima C. Guedes da Silva、Armando J. L. Pombeiro

  DOI：10.1021/om300020j

  日期：2012.3.26

  the structures of aminocarbene complexes 10 and 12 were elucidated by X-ray diffraction. The catalytic properties of 10–16 in the Suzuki–Miyaura cross-coupling of aryl halides, viz., 4-R2C6H4X (X = I, R2 = OMe; X = Br, R2 = Me, OMe, and NO2), with phenylboronic acid (in EtOH as solvent, K2CO3 or Cs2CO3 as base, 80 °C) yielding biaryl species 4-R2C6H4Ph, were evaluated. Complexes 14–16 exhibit a high

  金属结合的异腈之间的反应顺式- [的PdCl 2（CNR 1）2 ] [R 1 =环己基（CY）1，卜吨2，C 6 H ^ 4（2,6--ME 2）（的Xyl）3， CME 2 CH 2 CME 3 4 ]和1,3- diiminoisoindoline（9在CHCl）3在回流下4小时提供卡宾物种[钯 ç（N = C一（C 6 H ^ 4 CNH ñ b））= N （高）R1 } 2 ]一个- b（R 1 =赛扬10，82％分离产率）或顺式- [的PdCl Ç（N = C一（C 6 H ^ 4 CNH Ñ b））= N（H）R 1 }（ CNR 1）]一- b（R 1 =卜吨11，78％;的Xyl 12，84％; CME 2 CH 2 CME 3 13，79％），从添加的两个或一个所做的工作就是衍生9至起始1 - 4，分别。的相应的积分的顺式- [的PdCl 2（CNR 1）（PPH 3）（R
• Selective Nucleophilic Oxygenation of Palladium-Bound Isocyanide Ligands: Route to Imine Complexes That Serve as Efficient Catalysts for Copper-/Phosphine-Free Sonogashira Reactions
  作者：Andreii S. Kritchenkov、Konstantin V. Luzyanin、Nadezhda A. Bokach、Maxim L. Kuznetsov、Vladislav V. Gurzhiy、Vadim Yu. Kukushkin

  DOI：10.1021/om4000665

  日期：2013.3.25

  in excellent yields (90–94%), while the reaction of the cis-[PdCl2(CNR)2] complexes with aldonitrones proceeds as 1,3-dipolar cycloaddition, giving carbene adducts which then convert to the imine complexes. Theoretical calculations at the DFT level indicate that, in the case of aldonitrones, formation of the imine complexes occurs preferably via a cycloaddition/splitting pathway, including the generation

  顺式[PdCl 2（CNR）2 ]之间的金属介导反应（R = Xy（1），Cy（2），t Bu（3），C 6 H 3（Cl-2）Me-6（4））和酮基硝酮博士2 C = N（O）C 6 H ^ 4 R'（R'=我（5），CL（6））继续进行以1：1的摩尔比选择性亲核氧合，并提供该亚胺胩配合物[的PdCl 2 N（C 6 H ^ 4 R'）═CPh 2 }（CNR）]（7– 14：R'= Me，R = Xy（7），Cy（8），t Bu（9），C 6 H 3（Cl-2）Me-6（10）；R'= Cl，R = Xy（11），Cy（12），t Bu（13），C 6 H 3（Cl-2）Me-6（14）），产率极高（90-94％），而所述的反应顺式- [的PdCl 2（CNR）2 ]配合物醛硝酮以1,3-偶极环加成反应进行，生成卡宾加合物，然后将其转化为亚胺配合物。DFT水平的理论计算表明，在醛基亚
• Synthesis of Heterobimetallic Gold(I) Palladium(II) Bis(acyclic diaminocarbene) Complexes via the Isonitrile Route
  作者：Martin C. Dietl、Vanessa Vethacke、Ali Keshavarzi、Florian F. Mulks、Frank Rominger、Matthias Rudolph、Ibraheem A. I. Mkhalid、A. Stephen K. Hashmi

  DOI：10.1021/acs.organomet.2c00021

  日期：2022.3.28

  A convenient one-pot approach to bridged heterobimetallic gold(I) palladium(II) bis(acyclic diaminocarbene) complexes is presented. The methodology exploits the graduated nucleophilicities of aliphatic and aromatic amines connected via an aromatic unit. This enables a straightforward access to bridged complexes from easily available isonitrile metal precursors.

  提出了一种方便的一锅法桥接异质双金属金 (I) 钯 (II) 双（无环二氨基卡宾）配合物。该方法利用通过芳族单元连接的脂肪族胺和芳族胺的分级亲核性。这使得从容易获得的异腈金属前体中直接获得桥接络合物成为可能。