(iPr2PCH2CH2PiPr2)Pd(η(2)-HCCCH) | 194996-70-8

• 英文名称: (iPr2PCH2CH2PiPr2)Pd(η(2)-HCCCH)
• CAS: 194996-70-8
• 化学式: C₁₈H₃₄P₂Pd
• 分子量: 418.835
• InChiKey: HZWIFSYPFXQAFT-UHFFFAOYSA-N

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：

  (iPr2PCH2CH2PiPr2)Pd(η(2)-HCCCH) 、 2-Di(propan-2-yl)phosphanylethyl-di(propan-2-yl)phosphane;palladium(2+);prop-1-ene 以 乙醚 为溶剂， 以81%的产率得到[(iPr2PCH2CH2PiPr2)Pd]2(μ-(1,2-η(2)):(3,4-η(2))-HCCCCH)
  参考文献：
  名称：

  (R₂PC₂H₄PR₂)Pd⁰−1-Alkyne Complexes

  摘要：

  Displacement of the ethene ligand in (d(i)ppe)Pd(C2H4)(d(i)ppe = (Pr2PC2H4PPr2)-Pr-i-Pr-i) by 1-alkynes RC = CH affords the mononuclear complexes (d(i)ppe)Pd(RC = CH) (R = Me (2a), Ph (3a), CO2 Me (4), SiMe3 (5)). The molecular structure of 3a has been determined by X-ray crystallography. Mononuclear 2a and 3a have been reacted with stoichiometric amounts of (d(i)ppe)Pd(eta(1).C3H5)(2) as a source for [(d(i)ppe)Pd-0] to yield the dinuclear derivatives {(d(i)ppe)Pd}(2)(mu.RC = CH)(R = Me (2b), Ph (3b)). By the reaction of (d(i)ppe)Pd(C2H4) with difunctional vinylacetylene the mononuclear complex (d(i)ppe)Pd{(1,2-eta(2))-RC = CH} (R = CH = CH2 (6a)) is formed, which is in equilibrium with isomeric (d(i)ppe)Pd{(3,4-eta(2))-H2C = CHC = CH} (6b). Addition of [(d(i)ppe)Pd-0] to 6a,b yields dinuclear {(d(i)ppe)Pd}(2)(mu-RC = CH) (R = CH = CH2 (6c)). Reaction of (d(i)ppe)Pd(C2H4) with butadiyne affords (d(i)ppe)Pd(eta(2)-HC = CC = CH (7c). From d(i)ppe, Pt(cod)(2), and C4H2 the Pt homologue has also been synthesized and thus, together with the already known Ni derivative, the series (d(i)ppe)M(eta(2)-HC = CC CH (M = Ni (7a), Pd (7c), Pt (7f)) is now complete. When 7c and [(d(i)ppe)Pd-0] are combined, the dinuclear complex {(d(i)ppe)Pd}(2)(mu-RC = CH (R = C = CH) (7e)) is formed in solution, whereas isomeric {(d(i)ppe)Pd}(2){mu-(1,2-eta(2)):(3,4-eta(2))-HC = CC = CH} (7d) is present in the solid state. The preparation of the Pd-0-1-alkyne complexes refutes the conventional wisdom that this type of compound is inherently unstable. By reaction of (d(i)ppe)Pd(C2H4) with internal alkynes C2R2 the complexes (d(i)ppe)Pd(RC = CR) (R = Me (8a), Ph (9), CO2Me (10), SiMe3 (11)) have also been prepared. Combining 8a with [(d(i)ppe)Pd-0] affords dinuclear {(d(i)ppe)Pd}(2)(mu-MeC = CMe)(8b). Finally, solution thermolysis of 2b and 8b gives rise to dinuclear alkyne-free Pd-2(d(i)ppe)(2) (12).

  DOI：

  10.1021/om9702035
• 作为产物：
  描述：

  丁二炔 、 ((i)Pr2PC2H4P(i)Pr2)Pd(C2H4) 以 正戊烷 为溶剂， 以93%的产率得到(iPr2PCH2CH2PiPr2)Pd(η(2)-HCCCH)
  参考文献：
  名称：

  (R₂PC₂H₄PR₂)Pd⁰−1-Alkyne Complexes

  摘要：

  Displacement of the ethene ligand in (d(i)ppe)Pd(C2H4)(d(i)ppe = (Pr2PC2H4PPr2)-Pr-i-Pr-i) by 1-alkynes RC = CH affords the mononuclear complexes (d(i)ppe)Pd(RC = CH) (R = Me (2a), Ph (3a), CO2 Me (4), SiMe3 (5)). The molecular structure of 3a has been determined by X-ray crystallography. Mononuclear 2a and 3a have been reacted with stoichiometric amounts of (d(i)ppe)Pd(eta(1).C3H5)(2) as a source for [(d(i)ppe)Pd-0] to yield the dinuclear derivatives {(d(i)ppe)Pd}(2)(mu.RC = CH)(R = Me (2b), Ph (3b)). By the reaction of (d(i)ppe)Pd(C2H4) with difunctional vinylacetylene the mononuclear complex (d(i)ppe)Pd{(1,2-eta(2))-RC = CH} (R = CH = CH2 (6a)) is formed, which is in equilibrium with isomeric (d(i)ppe)Pd{(3,4-eta(2))-H2C = CHC = CH} (6b). Addition of [(d(i)ppe)Pd-0] to 6a,b yields dinuclear {(d(i)ppe)Pd}(2)(mu-RC = CH) (R = CH = CH2 (6c)). Reaction of (d(i)ppe)Pd(C2H4) with butadiyne affords (d(i)ppe)Pd(eta(2)-HC = CC = CH (7c). From d(i)ppe, Pt(cod)(2), and C4H2 the Pt homologue has also been synthesized and thus, together with the already known Ni derivative, the series (d(i)ppe)M(eta(2)-HC = CC CH (M = Ni (7a), Pd (7c), Pt (7f)) is now complete. When 7c and [(d(i)ppe)Pd-0] are combined, the dinuclear complex {(d(i)ppe)Pd}(2)(mu-RC = CH (R = C = CH) (7e)) is formed in solution, whereas isomeric {(d(i)ppe)Pd}(2){mu-(1,2-eta(2)):(3,4-eta(2))-HC = CC = CH} (7d) is present in the solid state. The preparation of the Pd-0-1-alkyne complexes refutes the conventional wisdom that this type of compound is inherently unstable. By reaction of (d(i)ppe)Pd(C2H4) with internal alkynes C2R2 the complexes (d(i)ppe)Pd(RC = CR) (R = Me (8a), Ph (9), CO2Me (10), SiMe3 (11)) have also been prepared. Combining 8a with [(d(i)ppe)Pd-0] affords dinuclear {(d(i)ppe)Pd}(2)(mu-MeC = CMe)(8b). Finally, solution thermolysis of 2b and 8b gives rise to dinuclear alkyne-free Pd-2(d(i)ppe)(2) (12).

  DOI：

  10.1021/om9702035