[palladium(II)(tert-butylisocyanide)2(η3-allyl)](perchlorate) | 1257394-22-1

• 英文名称: [palladium(II)(tert-butylisocyanide)2(η3-allyl)](perchlorate)
• 英文别名: [Pd(tert-butylisocyanide)2(allyl)]ClO4；[Pd(TIC)2(η3-C3H5)]ClO4；[Pd(TIC)2(C3H5)](ClO4)
• CAS: 1257394-22-1
• 化学式: C₁₃H₂₃N₂Pd*ClO₄
• 分子量: 413.21
• InChiKey: AHKDZMXEXQCQNT-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [palladium(II)(tert-butylisocyanide)2(η3-allyl)](perchlorate) 、 富马酸二甲酯 在 piperidine 作用下， 以 氘代氯仿 为溶剂， 生成 [Pd(TIC)2(η2-dmfu)]
  参考文献：
  名称：

  Synthesis, characterization, dynamics and reactivity toward amination of η³-allyl palladium complexes bearing mixed ancillary ligands. evaluation of the electronic characteristics of the ligands from kinetic data

  摘要：

  基于原始协议，我们合成了几种类型为[Pd(η3-C3H3R2)(LL′)]ClO4（R = H, Me; L, L′ = PPh3, P(OEt)3, 2,6-二甲基苯异氰酸酯, t-丁基异氰酸酯, 1,3-二美克基咪唑烷, 1,3-二美克基咪唑-2-亚氮烯）的配合物。其中一些配合物是全新的物质，经过充分表征，并通过1H NMR研究了它们在溶液中的行为。携带对称烯丙基部分的配合物[Pd(η3-C3H5)(LL′)]ClO4与哌啶在烯烃二甲基富马酸酯存在下的反应在动力学控制条件下进行了监测。观察到了烯丙基胺和钯(0)衍生物[Pd(η2-dmfu)(LL′)]的形成。反应速率k2被证明强烈依赖于辅助配体的性质，从而允许对配体的电子特性进行直接比较。确定的反应活性趋势主要受到辅助配体将电子密度传递到金属中心及随之影响到烯丙基片段的能力的影响。

  DOI：

  10.1039/c0dt00811g
• 作为产物：
  描述：

  sodium perchlorate monohydrate 、 bis(η3-allyl-μ-chloropalladium(II)) 、 异氰酸叔丁酯 以 二氯甲烷 为溶剂， 以88%的产率得到[palladium(II)(tert-butylisocyanide)2(η3-allyl)](perchlorate)
  参考文献：
  名称：

  A study on the insertion of isocyanides into palladium allyl bond: Effect of their nature on the strategic steps of the process

  摘要：

  The coordinative capabilities of tert-butyl isocyanide (TIC) and 2,6-dimethylphenyl isocyanide (DIC) were shown to be perfectly comparable in spite of their different steric and electronic features. As a matter of fact, when equimolar amounts of these two isocyanides are made to compete for the same coordination sites of a Pd-allyl substrate the statistical mixture of the possible products is always observed.On the contrary, the DIC proved to be much more efficient than TIC in promoting the migratory insertion of an allyl fragment. This conclusion was simply based on the analysis of the products resulting from the reaction of an appropriate Pd-allyl complex with both isocyanides simultaneously. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.06.055