Ni(II)(N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoimine)2 | 622784-51-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Ni(II)(N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoimine)2
• CAS: 622784-51-4
• 化学式: C₃₂H₅₀N₄NiO₄
• 分子量: 613.463
• InChiKey: BZEWRFPLXOLWNM-XCSIXQCQSA-L

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

• 作为反应物：
  描述：

  Ni(II)(N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoimine)2 在 NaH 、 air 作用下， 以 四氢呋喃 为溶剂， 生成 [(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：

  nickel(II) acetylacetonate 、 N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium 以 甲苯 为溶剂， 以81%的产率得到Ni(II)(N,N'-dineopentyl-2-amino-5-alcoholate-1,4-benzoquinonemonoimine)2
  参考文献：
  名称：

  A 6π + 6π Potentially Antiaromatic Zwitterion Preferred to a Quinoidal Structure:  Its Reactivity Toward Organic and Inorganic Reagents

  摘要：

  A straightforward synthesis of the zwitterionic benzoquinonemonoimine 8 is reported. This molecule is a rare example of a zwitterion being more stable than its canonical forms. It is shown that 8 is best described as constituted of two chemically connected but electronically not conjugated 6 pi electron subunits. Its reactivity with electrophiles such as H+, CH3+, and metal salts leads to the synthesis of new 12,7 electron molecules 12 (H+), 14 (CH3+), and 20 (Pd2+), respectively, in which one or both 6 pi electron subsystems localize into an alternation of single and double bonds, as established by X-ray diffraction. The acidity of the N-H protons of 8 can be modulated by an external reagent. Dependent on the electrophile used, the control of the pi system delocalization becomes possible. When the electrophile simply adds to the zwitterion as in 12, 14, or 15, there is no more negative charge to be delocalized and only the positive charge remains delocalized between the nitrogen atoms. Furthermore, when a reaction with the electrophilic reagent results in deprotonation, as in 17-21, there remains no charge in the system to be delocalized. DFT calculations were performed on models of 8, 12, 14, 20, and on other related zwitterions 9 and 10 in order to examine the influence of the fused cycles on the charge separation and on the singlet-triplet energy gap. An effect of the nitrogen substituents in 8 is to significantly stabilize the singlet state. The dipole moment of 8 was measured to be 9.7 D in dichloromethane, in agreement with calculated values. The new ligands and complexes described in this article constitute new classes of compounds relevant to many areas of chemistry.

  DOI：

  10.1021/ja0354622