[PdCl(η3-1,1',3,3'-tetramethylpropadiene)] | 177740-62-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: [PdCl(η3-1,1',3,3'-tetramethylpropadiene)]
• 英文别名: [PdCl(η(3)-(Me)2CC(Me)C(Me)2)]2；[PdCl(η(3)-CMe2C(Me)CMe2)]2；[Pd2(μ-Cl)2(η3-1,1,2,3,3-Me5C3)2]；chloropalladium(1+);2,3,4-trimethylpent-2-ene
• CAS: 177740-62-4
• 化学式: C₁₆H₃₀Cl₂Pd₂
• 分子量: 506.16
• InChiKey: LVEUUAPPDXQWTI-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [PdCl(η3-1,1',3,3'-tetramethylpropadiene)] 、 2-(diphenylphosphino)-benzylidene-S(-)-α-methyl-benzylamine 以 二氯甲烷 为溶剂， 生成 [Pd(η(3)-CMe2C(Me)CMe2)(2-(diphenylphosphino)-benzylidene-S(-)-α-methyl-benzylamine)][Cl]
  参考文献：
  名称：

  Methyl-, acetyl- and allyl-palladium and -piatinum complexes containing the novel chiral phosphorus-imine 2-(diphenylphosphino)-benzylidene-S( − )-α-methyl-benzylamine ligand

  摘要：

  Neutral compounds of the type [MX(2)(L)] and [MX(Me)(L)] and ionic complexes of the type [M(Me)(L)](O3SCF3), in which X = Cl, Br, I; M = Pd, Pt; L = 2-(diphenylphosphino)-benzylidene-S(-)-alpha-methyl-benzylamine, have been prepared and characterized. Single crystal X-ray determinations of [PdCl2(L)] (1a) and [PtI2(L)] (3b) showed, in both cases, a chelate coordination of the PN ligand thereby forming a six-membered ring. The square planar surrounding is completed by the two halide atoms. The single crystal X-ray determination of [PdCl(Me)Cl(L)] (4a) shows an analogous geometry with a chelating PN ligand, a chloride atom and a methyl group, which is positioned cis to the phosphorus atom, completes the square planar surrounding. The methylpalladium and -platinum complexes reacted with CO to give the corresponding acetyl complexes. The insertion rates increased in the order Cl < Br < O3SCF3- while the reaction is first order in metal complex and first order in CO concentration. Complexes [Pd(eta(3)-allyl)(PN)]Y-+(-) (Y = Cl, O3SCF3) with symmetric allyl groups 2-RC(3)H(5) (R = Me, C(O)Me), 2-MeC(3)Me(4) and asymmetrically substituted allyl groups 2-R-C(3)H(2)Me(2) (R = H, Me) have been prepared Temperature dependent H-1, P-31{H-1} and C-13{H-1} NMR has been used to determine the influence of the chiral ligand on the structural aspects and dynamic features. It is shown that a delicate balance between counteracting steric and electronic factors determines the type of isomer, i.e. with the P atom cis or trans to the CMe(2) moiety of the asymmetric allyl group.

  DOI：

  10.1016/s0020-1693(96)05307-8
• 作为产物：
  描述：

  2,4-二甲基-2,3-戊二烯 、 chloromethyl(1,5-cyclooctadiene)palladium(II) 以 二氯甲烷 为溶剂， 以85%的产率得到[PdCl(η3-1,1',3,3'-tetramethylpropadiene)]
  参考文献：
  名称：

  Ankersmit, Hubertus A.; Veldman, Nora; Spek, Anthony L., Inorganica Chimica Acta, 1996, vol. 252, # 1-2, p. 203 - 219

  摘要：

  DOI：

文献信息

• The marked influence of steric and electronic properties of ancillary pyridylthioether ligands on the rate of allene insertion into the palladium–carbon bond
  作者：Luciano Canovese、Fabiano Visentin、Gavino Chessa、Claudio Santo、Paolo Uguagliati、Giuliano Bandoli

  DOI：10.1016/s0022-328x(02)01145-2

  日期：2002.5

  has been studied by 1H-NMR and UV–vis techniques. The rate of reaction appears to be strongly influenced by the steric and electronic properties of the ancillary ligand. The distortion induced by the substituent R′ in position 6 of the pyridine ring on the main coordination plane of the substrate (allowed by sulphur sp3 hybridisation) renders the substrate itself more prone to nucleophilic attack by the

  合成了含有吡啶硫基醚辅助配体（R'NSR）（R'= H，Me，Cl; R = Me，Et，i -Pr，t -Bu，Ph）的中性甲基和酰基钯氯络合物，并合成通过元素分析和光谱学方法表征。1 H-NMR和UV-vis技术研究了这些络合物对插入钯-碳键中的丙二烯的反应性（丙二烯= DMA = 1,1-二甲基丙二烯； TMA = 1,1,3,3-四甲基丙二烯）。反应速率似乎受辅助配体的空间和电子性质强烈影响。由底物主配位平面上吡啶环6位上的取代基R'引起的形变（由硫SP 3允许）杂交）使底物本身更容易受到丙二烯的亲核攻击。通过降低NS部分中螯合原子的碱度，可进一步提高丙二烯插入的速率，这会导致钯核的亲电性增加，因此，在含有配体的配合物的情况下，测得的速率常数到目前为止，对于类似的反应，6-氯-2-苯基硫代甲基吡啶（ClN = SPh）是最大的。此外，在详尽研究所有相关吡啶基硫醚甲基配合物的行为
• Stepwise Successive Insertion of Carbon Monoxide and Allenes into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(<i>p</i>-anisylimino)acenaphthene
  作者：Johannes H. Groen、Cornelis J. Elsevier、Kees Vrieze、Wilberth J. J. Smeets、Anthony L. Spek

  DOI：10.1021/om960163p

  日期：1996.7.23

  CF3 (13b). The novel complexes 9−12 are the first isolated and fully characterized complexes formed by successive insertion reactions of carbon monoxide and allenes, while 13a is the first isolated complex containing a metal-bonded ter-oligomer of carbon monoxide, an allene, and norbornadiene. The X-ray crystal structure of 7a has been determined and shows a distorted square pyramidal geometry in which

  丙二烯，3-甲基-1,2-丁二烯（DMA）和2,4-二甲基-2,3-戊二烯（TMA）通过迁移插入与中性和离子Pd（R）X（p -An-BIAN）反应）（R =我（1），C（O）Me（2）; X = Cl（上一个），SO 3 CF 3（b））的复合物，含有该刚性配体氮双（p -anisylimino）苊（p -一个扁），从而导致新的，稳定的络合物烯丙基钯的Pd（η 3 -C 3 H ^ 4 R）X（p -一个扁）（R =我（3），C（O）Me（6）），加入Pd（η 3 -C 5ħ 8 R）X（p -一个扁）（R =我（4），C（O）Me（7）），和Pd（η 3 -C 7 ħ 12 R）X（p -一个扁） （R ＝ Me（5），C（O）Me（8））分别（X ＝ Cl（a），SO 3 CF 3（b））。中性配合物6a和7a与一氧化碳反应形成酰钯配合物Pd（C（O）C 3 H 4 C（O）Me）Cl（p
• Stable Palladium(0), Palladium(II), and Platinum(II) Complexes Containing a New, Multifunctional and Hemilabile Phosphino−Imino−Pyridyl Ligand:  Synthesis, Characterization, and Reactivity
  作者：Richard E. Rülke、Vincent E. Kaasjager、Petra Wehman、Cornelis J. Elsevier、Piet W. N. M. van Leeuwen、Kees Vrieze、Jan Fraanje、Kees Goubitz、Anthony L. Spek

  DOI：10.1021/om9509047

  日期：1996.6.25

  e)(2-(2-pyridyl)ethyl)amine, PNN, containing phosphine, imine, and pyridyl donor groups and alkyl-, allyl-, and acylpalladium complexes, methylplatinum complexes, and a zerovalent palladium complex containing PNN have been synthesized and characterized with 1H-, 13C-, 31P-, and 15N-NMR. PNN commonly coordinates in a terdentate fashion, resulting in ionic complexes of the type [(PNN)MII(R)]Y (M = Pd

  新型的多功能半不稳定的磷-双（氮）配体N-（2-（二苯基膦基）亚苄基）（2-（2-吡啶基）乙基）胺，PNN，包含膦，亚胺和吡啶基供体基团和烷基-，烯丙基和酰基铝配合物，甲基铂配合物和含PNN的零价钯配合物已经合成，并通过1 H-，13 C-，31 P-和15 N-NMR进行了表征。PNN通常以齿状方式进行配位，从而生成[（PNN）M II（R）] Y类型的离子络合物（M = Pd，Pt，R = CH 3，Y = Cl，CF 3 SO 3； M = Pd ，R = C（O）CH 3，Y = CF 3SO 3 ; M =钯，R =η 1 -CH 2 C（H）CH 2，Y =氯，CF 3 SO 3）。PNN的二齿配位是观察[（PNN）的Pd II（η 3 - （CH 3）2 CC（CH 3）C（CH 3）2）] Cl和令人惊奇地也为中性（PNN）的Pd II（C（O CH 3）（Cl）。分离出了前所未有的零价钯络合物（PNN）Pd