trans-bromo(bis(triphenylphosphine))(3-ethoxy-3-oxy-1-propinyl)palladium(II) | 1322001-87-5

• 英文名称: trans-bromo(bis(triphenylphosphine))(3-ethoxy-3-oxy-1-propinyl)palladium(II)
• CAS: 1322001-87-5
• 化学式: C₄₁H₃₅BrO₂P₂Pd
• 分子量: 807.999
• InChiKey: PBIDTPUCBLLDDZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None

反应信息

• 作为反应物：
  描述：

  二氯甲烷 、 trans-bromo(bis(triphenylphosphine))(3-ethoxy-3-oxy-1-propinyl)palladium(II) 、 三氟甲烷磺酸甲酯 以 乙腈 为溶剂， 以96%的产率得到trans-(acetonitrile)(3-ethoxy-3-oxy-1-propinyl)palladium(II) trifluoromethylsulfonate dichloromethane monosolvate
  参考文献：
  名称：

  Platinum allenylidene complexes and formation of platinum and palladium acetonitrile alkynyl complexes

  摘要：

  The platinum(0) complex [Pt(PPh3)(4)] reacts with brominated propargylic amides and esters in benzene by oxidative addition to give trans-[Br(PPh3)(2)Pt-C C-C(=O)R] complexes whereas no reaction occurs when halogenated solvents (CH2Cl2, CHCl3) are used. The cis-ligands PPh3 can be replaced by P(Pr-i)(3) and the bromide by trifluoroacetate. O-Alkylation of those trans-[X(PR'(3))(2)Pt-C C-C(=O)R] complexes (X = Br, CF3COO; R' = Ph, Pr-i) derived from propargylic amides with MeOTf or [Me3O]BF4 in CH2Cl2 gives the first cationic monoallenylidene complexes of platinum, trans-[X(PR'(3))(2)Pt=C=C=C(OMe)NR2](+) Y (Y = OTf, BF4). In contrast, trans-[Br(PPh3)(2)Pt-C C-C(=O)OMenthyl] derived from a propargylic ester does not react with MeOTf in CH2Cl2. However, in acetonitrile instead of O-methylation the substitution of acetonitrile for the bromide ligand to yield the cationic acetonitrile alkynyl platinum complex trans-[MeCN(PPh3)(2)Pt-C C-C(=O)OMenthyl](+) OTf is observed. The related palladium complexes trans-[X(PR'(3))(2)Pd-C C-C(=O)OR] (X = Br, CF3COO; R' = Ph, Pr-i, R = menthyl, Et) react with MeOTf or [Et3O]BF4 analogously affording trans-[MeCN(PR'(3))(2)Pd-C C-C(=O)OR](+) Y (Y = OTf, BF4). (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.02.074
• 作为产物：
  描述：

  四(三苯基膦)钯 、 3-溴丙酸乙酯 以 二氯甲烷 为溶剂， 以89%的产率得到trans-bromo(bis(triphenylphosphine))(3-ethoxy-3-oxy-1-propinyl)palladium(II)
  参考文献：
  名称：

  Platinum allenylidene complexes and formation of platinum and palladium acetonitrile alkynyl complexes

  摘要：

  The platinum(0) complex [Pt(PPh3)(4)] reacts with brominated propargylic amides and esters in benzene by oxidative addition to give trans-[Br(PPh3)(2)Pt-C C-C(=O)R] complexes whereas no reaction occurs when halogenated solvents (CH2Cl2, CHCl3) are used. The cis-ligands PPh3 can be replaced by P(Pr-i)(3) and the bromide by trifluoroacetate. O-Alkylation of those trans-[X(PR'(3))(2)Pt-C C-C(=O)R] complexes (X = Br, CF3COO; R' = Ph, Pr-i) derived from propargylic amides with MeOTf or [Me3O]BF4 in CH2Cl2 gives the first cationic monoallenylidene complexes of platinum, trans-[X(PR'(3))(2)Pt=C=C=C(OMe)NR2](+) Y (Y = OTf, BF4). In contrast, trans-[Br(PPh3)(2)Pt-C C-C(=O)OMenthyl] derived from a propargylic ester does not react with MeOTf in CH2Cl2. However, in acetonitrile instead of O-methylation the substitution of acetonitrile for the bromide ligand to yield the cationic acetonitrile alkynyl platinum complex trans-[MeCN(PPh3)(2)Pt-C C-C(=O)OMenthyl](+) OTf is observed. The related palladium complexes trans-[X(PR'(3))(2)Pd-C C-C(=O)OR] (X = Br, CF3COO; R' = Ph, Pr-i, R = menthyl, Et) react with MeOTf or [Et3O]BF4 analogously affording trans-[MeCN(PR'(3))(2)Pd-C C-C(=O)OR](+) Y (Y = OTf, BF4). (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.02.074