{(η5-η1-η5-η1-meso-octaethylporphyrinogen)zirconium(THF)} | 136396-52-6

• 英文名称: {(η5-η1-η5-η1-meso-octaethylporphyrinogen)zirconium(THF)}
• CAS: 136396-52-6；148420-64-8；214468-22-1
• 化学式: C₄₀H₅₆N₄OZr
• 分子量: 700.135
• InChiKey: LVXWSBWNEYVCRP-UHFFFAOYSA-N

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：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  {(η5-η1-η5-η1-meso-octaethylporphyrinogen)zirconium(THF)} 、 sodium hydride 以 甲苯 为溶剂， 以78%的产率得到{((η5-η1-η5-η1-meso-octaethylporphyrinogen)zirconium)2(μ-NaH)2}
  参考文献：
  名称：

  Zirconium meso-octaethylporphyrinogen as a carrier for sodium hydride in toluene: zirconium-sodium bimetallic hydride and alkyls

  摘要：

  The reaction of the tetralithium meso-octaethylporphyrinogen Et8N4Li4(THF)4 (2) with ZrCl4(THF)2 led to the formation of [(eta5-eta1-eta5-eta1-Et8N4)Zr(THF)] (3), containing two eta5 and two eta1 pyrrolyl anions bonded to zirconium. Such a complex acts as a bifunctional acid-base system able to dissolve ionic salts in their monomeric or dimeric form in hydrocarbon solution. The reaction of 3 with NaH in toluene led to the complexation of NaH via the interaction of the hydride with the Lewis acid Zr and the eta5 complexation of Na by the pyrrolyl anions in [{eta5-eta1-eta1-eta1-Et8N4)-Zr}2(mu-NaH)2] (4). Complex 4 reacts with terminal olefins in toluene by inserting the C=C double bond in the Zr-H functionality and so forming, in the case of ethylene, [{eta5-eta1-eta1-eta1-Et8N4)Zr(CH2CH3)}2(mu-Na)2] (5) and, in the case of 1-hexene, [{eta5-eta1-eta1-eta1-Et8N4)Zr(CH2(CH2)4CH3)}2(mu-Na)2] (6). Similarly, 4 adds to PhC=CH, which leads to the corresponding vinyl complex [(eta5-eta1-eta1-eta1-Et8N4)Zr-trans-(CH=CHPh)]2 (7). The dimeric structure of 4 remains intact after the reaction giving 5-7, however, in these products, major differences in the Na-porphyrinogen interaction modes can be seen. The reaction of 4 with C2H4 in THF led to a Zr-H porphyrinogen monomeric species identical to that formed from dissolving 5 in THF, [{(eta5-eta1-eta1-eta1-Et8N4)Zr(CH2CH3)}{Na(THF)2}] (8). Crystallographic details: 3 orthorhombic, space group Pbcn, a = 12.935(3) angstrom, b = 12.704(3) angstrom, c = 21.649(3) angstrom, alpha = beta = gamma 90-degrees, Z = 4, R = 0.037; 4 monoclinic, space group C2/c, a = 24.272(3) angstrom, b = 12.640(4) angstrom, c = 21.886(3) angstrom, alpha = gamma = 90-degrees, beta = 101.75(1)degrees, Z = 4, R = 0.053; 5 triclinic, space group P1BAR, a = 11.565(2) angstrom, b = 12.598(2) angstrom, c = 14.327(2) angstrom, alpha = 100.30(1)degrees, beta = 103.65(1)degrees, gamma = 113.73(1)degrees, Z = 1, R = 0.034; 7 monoclinic, space group P2(1)/c, a = 13.815(2) angstrom, b = 24.619(2) angstrom, c = 13.981(2) angstrom, alpha = gamma = 90-degrees, beta = 108.73(1)degrees, Z = 2, R = 0.047; 8 monoclinic, space group P2(1)/c, a = 11.264(1) angstrom, b = 19.646(4) angstrom, c = 20.609(3) angstrom, alpha = gamma = 90-degrees, beta = 101.18(2)degrees, Z = 4, R = 0.042.

  DOI：

  10.1021/ja00062a024
• 作为产物：
  描述：

  zirconium chloride-tetrahydrofuran 、 tetralithium meso-octaethylporphyrinogen*4THF 以 甲苯 为溶剂， 以95%的产率得到{(η5-η1-η5-η1-meso-octaethylporphyrinogen)zirconium(THF)}
  参考文献：
  名称：

  Zirconium meso-octaethylporphyrinogen as a carrier for sodium hydride in toluene: zirconium-sodium bimetallic hydride and alkyls

  摘要：

  The reaction of the tetralithium meso-octaethylporphyrinogen Et8N4Li4(THF)4 (2) with ZrCl4(THF)2 led to the formation of [(eta5-eta1-eta5-eta1-Et8N4)Zr(THF)] (3), containing two eta5 and two eta1 pyrrolyl anions bonded to zirconium. Such a complex acts as a bifunctional acid-base system able to dissolve ionic salts in their monomeric or dimeric form in hydrocarbon solution. The reaction of 3 with NaH in toluene led to the complexation of NaH via the interaction of the hydride with the Lewis acid Zr and the eta5 complexation of Na by the pyrrolyl anions in [{eta5-eta1-eta1-eta1-Et8N4)-Zr}2(mu-NaH)2] (4). Complex 4 reacts with terminal olefins in toluene by inserting the C=C double bond in the Zr-H functionality and so forming, in the case of ethylene, [{eta5-eta1-eta1-eta1-Et8N4)Zr(CH2CH3)}2(mu-Na)2] (5) and, in the case of 1-hexene, [{eta5-eta1-eta1-eta1-Et8N4)Zr(CH2(CH2)4CH3)}2(mu-Na)2] (6). Similarly, 4 adds to PhC=CH, which leads to the corresponding vinyl complex [(eta5-eta1-eta1-eta1-Et8N4)Zr-trans-(CH=CHPh)]2 (7). The dimeric structure of 4 remains intact after the reaction giving 5-7, however, in these products, major differences in the Na-porphyrinogen interaction modes can be seen. The reaction of 4 with C2H4 in THF led to a Zr-H porphyrinogen monomeric species identical to that formed from dissolving 5 in THF, [{(eta5-eta1-eta1-eta1-Et8N4)Zr(CH2CH3)}{Na(THF)2}] (8). Crystallographic details: 3 orthorhombic, space group Pbcn, a = 12.935(3) angstrom, b = 12.704(3) angstrom, c = 21.649(3) angstrom, alpha = beta = gamma 90-degrees, Z = 4, R = 0.037; 4 monoclinic, space group C2/c, a = 24.272(3) angstrom, b = 12.640(4) angstrom, c = 21.886(3) angstrom, alpha = gamma = 90-degrees, beta = 101.75(1)degrees, Z = 4, R = 0.053; 5 triclinic, space group P1BAR, a = 11.565(2) angstrom, b = 12.598(2) angstrom, c = 14.327(2) angstrom, alpha = 100.30(1)degrees, beta = 103.65(1)degrees, gamma = 113.73(1)degrees, Z = 1, R = 0.034; 7 monoclinic, space group P2(1)/c, a = 13.815(2) angstrom, b = 24.619(2) angstrom, c = 13.981(2) angstrom, alpha = gamma = 90-degrees, beta = 108.73(1)degrees, Z = 2, R = 0.047; 8 monoclinic, space group P2(1)/c, a = 11.264(1) angstrom, b = 19.646(4) angstrom, c = 20.609(3) angstrom, alpha = gamma = 90-degrees, beta = 101.18(2)degrees, Z = 4, R = 0.042.

  DOI：

  10.1021/ja00062a024

文献信息

• The π-Pyrrole Complexation of Alkali Metal Ions by Zirconiummeso-Octaalkylporphyrinogens: Encapsulation of Li4H4 and Li2O in Sandwich Structures
  作者：Carlo Floriani、Euro Solari、Giovanna Solari、Angiola Chiesi-Villa、Corrado Rizzoli

  DOI：10.1002/(sici)1521-3773(19980904)37:16<2245::aid-anie2245>3.0.co;2-j

  日期：1998.9.4

  Complexation of metal ion and counterion by the same compound is possible with zirconium meso-octaalkylporphyrinogens (structure of a dimeric complex with four encapsulated equivalents of LiH is depicted): they carry salts in the molecular ion-pair form in hydrocarbons, and function as acid-base bifunctional compounds.
• Bifunctional Carriers of Alkali-Metal Enolates:  The Use of Zirconium <i>meso</i>-Octaethylporphyrinogen in Aldol Condensation Reactions
  作者：Giovanna Solari、Euro Solari、Carlo Floriani、Angiola Chiesi-Villa、Corrado Rizzoli

  DOI：10.1021/om9609325

  日期：1997.2.1

  The (meso-octaethylporphyrinogenato)zirconium(IV) species [(Et(8)N(4))Zr(thf)] (1) binds the acetophenone potassium enolate [PhCOCH(2)K] (2) in its ion-pair form, [(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))ZrPhC(CH2)O}K(thf)(3)] (3), and thus drives the aldol condensation reaction with acetophenone. The resulting aldolate, which occurs in a metallacyclic form due to the solvation of potassium by a phenyl ring, remains eta(1) (O)-bonded to zirconium, [(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))ZrPhC(CH2)OC(O)C(Me)Ph}K](n) (4).