trans-Cl(Et3P)2Pd[C(Cl)=PN(SiMe3)2] | 217309-75-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: trans-Cl(Et3P)2Pd[C(Cl)=PN(SiMe3)2]
• 英文别名: [bis(trimethylsilyl)amino]phosphanylidene-chloromethane;chloropalladium(1+);triethylphosphane
• CAS: 217309-75-6
• 化学式: C₁₉H₄₈Cl₂NP₃PdSi₂
• 分子量: 617.015
• InChiKey: MXIGWMKHRCLVLZ-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：
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反应信息

• 作为产物：
  描述：

  tris(triethylphosphine)ppalladium(0) 、 phosphan 以 正己烷 为溶剂， 生成 trans-Cl(Et3P)2Pd[C(Cl)=PN(SiMe3)2]
  参考文献：
  名称：

  Palladium Coordination Compounds of σ³λ⁵-Phosphoranes:  First Examples of Phosphonio−Methylene(imino)metallophosphorane [(R₃P)(Me₃Si)CP(ML_n)NSiMe₃] and Phosphonio−Methylene(oxo)phosphorane [(R₃P)(Me₃Si)CP(O)NSiMe₃] Ligands

  摘要：

  The oxidative addition reaction of Pd(PPh3)(4) with Cl2C=PN(SiMe3)(2) forms the phosphavinyl phosphonium complex Cl(Ph3P)Pd[eta(2)-C(Cl)(PPh3)=PN(SiMe3)(2)] (IIIa), which results from PPh3 migration from Pd to carbon in the eta(1)-phosphavinyl intermediate trans-Cl(Ph3P)(2)Pd-[C(Cl)=PN(SiMe3)(2)] (IIa). The reaction of Pd(dba)(dppe) with Cl2C=PN(SiMe3)(2) forms the eta(1)-phosphavinyl complex cis-Cl(dppe)Pd[C(Cl)=PN(SiMe3)(2)] (VI), which does not undergo phosphine migration. Compound IIIa undergoes substitution of the chloride ligand by PPh3 or MeCN in the presence of KPF6 to generate [(Ph3P)(2)Pd(eta(2)-C(Cl)(PPh3)=PN(SiMe3)(2))] (PF6) (IV) or [(Ph3P)(MeCN)Pd(eta(2)-C(Cl)(PPh3)=PN(SiMe3)(2))](PF6) (V), respectively; the structure of V was determined by X-ray diffraction studies. The reaction of Pd(PEt3)(4) with Cl2C= PN(SiMe3)(2) forms the eta(1)-phosphavinyl complex trans-Cl(Et3P)(2)Pd[C(Cl)=PN(SiMe3)(2)] (IIb), which does not undergo PEt3 migration. When 2 equiv of Pd(PEt3)(4) are reacted with Cl2C= PN(SiMe3)(2) the phosphonio-methylene(imino)metallophosphorane complex Pd(PEt3)(Cl)[mu-eta(1):eta(2)-C(SiMe3)(PEt3)=P=N(SiMe3)]Pd(PEt3)Cl (VIIa-b) forms as a 1:1 isomeric mixture. Compound VIIa-b reacts with MeI or NaI to generate Pd(PEt3)(I)[mu-eta(1):eta(2)-C(SiMe3)(PEt3)= P=N(SiMe3)]Pd(PEt3)I (VIIIa-b) and reacts with traces of water to generate Cl(Et3P)Pd-[eta(2)-C(SiMe3)(PEt3)=P(=O)NH(SiMe3)] (IX). The structure of VIIIb was partially determined, and the structure of IX was determined by X-ray diffraction studies. Compounds VIIa-b, VIIIa-b, and IX exhibit the first examples of coordinated methylene(imino, oxo)phosphorane ligands.

  DOI：

  10.1021/om9801913