(8-methylenequinoline)Pd(II)(N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoimine) | 797816-73-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: (8-methylenequinoline)Pd(II)(N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoimine)
• CAS: 797816-73-0
• 化学式: C₂₆H₃₃N₃O₂Pd
• 分子量: 525.987
• InChiKey: CKKZELFELACJKO-JKXROLASSA-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：

  [Pd(8-methylenequinoline)(μ-Cl)]2 、 (8-methylenequinoline)Pd(II)(N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoimine) 在 NaH 作用下， 以 四氢呋喃 为溶剂， 以85%的产率得到[(8-methylenequinoline)Pd(II)]2(N,N'-dineopentyl-5-alcoholate-1,2,4-benzoquinonediimine)
  参考文献：
  名称：

  Stepwise Synthesis, Structures, and Reactivity of Mono-, Di-, and Trimetallic Metal Complexes with a 6π + 6π Quinonoid Zwitterion

  摘要：

  The benzoquinonemonoimine N, N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium [C6H2( -NHCH(2)tBu)(2)( -O)(2)] 6, which is a rare example of an organic zwitterion being more stable than its canonical form, is best described as constituted of two chemically connected but electronically not conjugated 6pi electron subunits. The two successive acidities of 6 allow the preparation of mono-, di-, and trimetallic complexes in which the control of the pi-system delocalization becomes possible. Reaction of 6 with NaOt-Bu results in monodeprotonation of one N-H function, and the isolated sodium salt 9, which is stable under N-2, reacts with chloride-bridged Pd(II) homodimetallic complexes, [AuCl(PPh3)] or trans-[NiCl(Ph)(PPh3)(2)], to afford the monometallic complexes 10-15 in which the pi-system is localized. A second in situ deprotonation of the remaining N-H amino function of 10 with NaH followed by reaction with [Pd(8-mq)(mu-Cl)](2) (8-mq = orthometalated 8-methylquinoline) affords the homodimetallic complex 17 in which the pi-system of the quinonoid ligand is delocalized between the two metal centers. Deprotonation of both N-H amino functions of the square-planar complex trans-[Ni(N,O)(2)] 15 with NaH and reaction with [Pd(8-mq)(mu-Cl)]2 affords the heterotrimetallic (Pd, Ni, Pd) complex 18 in which the pi-system of the two quinonoid ligands is delocalized between the three metal centers. The crystal structures of the monometallic complexes 10 and 13 and of the dipalladium complex 17 are reported and consequences of metal coordination discussed. Complex 15 was tested in catalytic ethylene oligomerization with AlEtCl2 as cocatalyst.

  DOI：

  10.1021/ic049263a
• 作为产物：
  描述：

  [Pd(8-methylenequinoline)(μ-Cl)]2 在 NaH 、 air 作用下， 以 四氢呋喃 为溶剂， 生成 (8-methylenequinoline)Pd(II)(N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoimine)
  参考文献：
  名称：

  Stepwise Synthesis, Structures, and Reactivity of Mono-, Di-, and Trimetallic Metal Complexes with a 6π + 6π Quinonoid Zwitterion

  摘要：

  The benzoquinonemonoimine N, N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium [C6H2( -NHCH(2)tBu)(2)( -O)(2)] 6, which is a rare example of an organic zwitterion being more stable than its canonical form, is best described as constituted of two chemically connected but electronically not conjugated 6pi electron subunits. The two successive acidities of 6 allow the preparation of mono-, di-, and trimetallic complexes in which the control of the pi-system delocalization becomes possible. Reaction of 6 with NaOt-Bu results in monodeprotonation of one N-H function, and the isolated sodium salt 9, which is stable under N-2, reacts with chloride-bridged Pd(II) homodimetallic complexes, [AuCl(PPh3)] or trans-[NiCl(Ph)(PPh3)(2)], to afford the monometallic complexes 10-15 in which the pi-system is localized. A second in situ deprotonation of the remaining N-H amino function of 10 with NaH followed by reaction with [Pd(8-mq)(mu-Cl)](2) (8-mq = orthometalated 8-methylquinoline) affords the homodimetallic complex 17 in which the pi-system of the quinonoid ligand is delocalized between the two metal centers. Deprotonation of both N-H amino functions of the square-planar complex trans-[Ni(N,O)(2)] 15 with NaH and reaction with [Pd(8-mq)(mu-Cl)]2 affords the heterotrimetallic (Pd, Ni, Pd) complex 18 in which the pi-system of the two quinonoid ligands is delocalized between the three metal centers. The crystal structures of the monometallic complexes 10 and 13 and of the dipalladium complex 17 are reported and consequences of metal coordination discussed. Complex 15 was tested in catalytic ethylene oligomerization with AlEtCl2 as cocatalyst.

  DOI：

  10.1021/ic049263a