lithium;butane;5,5,10,10,15,15,20,20-octaethylporphyrin-21,22,23,24-tetraide;oxolane;zirconium(4+) | 170801-86-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: lithium;butane;5,5,10,10,15,15,20,20-octaethylporphyrin-21,22,23,24-tetraide;oxolane;zirconium(4+)
• CAS: 170801-86-2
• 化学式: C₄₈H₇₃LiN₄O₂Zr
• 分子量: 836.298
• InChiKey: NFZRLBDABIMVFF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.47
• 重原子数：
  56
• 可旋转键数：
  9
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  22.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  四氢呋喃 、 正丁基锂 、 meso-octaethylporphyrinogen-zirconium(IV)*THF 以 四氢呋喃 、 甲苯 为溶剂， 以80%的产率得到lithium;butane;5,5,10,10,15,15,20,20-octaethylporphyrin-21,22,23,24-tetraide;oxolane;zirconium(4+)
  参考文献：
  名称：

  Bifunctional Carriers of Organometallic Functionalities: Alkali-Metal-Zirconium-Hydrido, -Alkyl, and -Allyl Derivatives of meso-Octaethylporphyrinogen and Their Reaction with Isocyanides

  摘要：

  The reaction of alkali-metal organometallics with the meso-octaethylporphyrinogenzirconium complex [(eta(5):eta(1):eta(5):eta(1):-Et(8)N(4))Zr(THF)] (1), acting as a bifunctional carrier, led to the formation of bimetallic K-Zr and Li-Zr organometallics. Such compounds formed from the addition of the nucleophilic fragment to zirconium, while the alkali-metal cation remained bonded to the electron-rich periphery of the porphyrinogen moiety. The addition of ICE to 1 in a 1:1 molar ratio led to the formation of the dinuclear complex [{(eta(5):eta(1):eta(1):eta(1):-Et(8)N(4))Zr}(2)-{mu-KH}(2)] (2), while with a large excess of KH under controlled conditions we obtained a tetranuclear polyhydride species, [{(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Zr}(4){KH}(8) .(THF)(10)], (3), having the [Zr4K4H8] skeleton containing both mu(2)- and mu(3)-hydrides. In toluene-THF, the addition of LiR to 1 gave the monomeric dimetallic lithium-zirconium alkyls [{(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Zr-R}{Li(THF)(2)}] (R = Me, 4; R = Bu(t), 5). The reaction of 1 with potassium allyl gave a structurally complex, bimetallic, polynuclear compound where the allyl fragment interacts in both an eta(1) and eta(2) fashion, with zirconium and potassium, respectively, to give complex 6, [(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Zr(mu-eta(3)-C3H5)K](n) Other potassium-zirconium alkyl derivatives are accessible via: (i) the hydrozirconation of olefins using complex 2 (the reaction of 2 with ethylene gave [{(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Zr-CH2CH3}(2)(mu-K)(2)] (7)) and (ii) the exchange of the alkali-metal cation (the reaction of 4 with KH led to the corresponding KMe. derivative supported by 1, [{(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Zr-Me}{K(THF)}(2)] (8)). The bimetallic K-Zr alkyl and hydride derivatives are very reactive in insertion reactions. The reaction of 2 and 4 with Bu(t)NC led respectively, to the corresponding eta(2)-iminoformyl [{(eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Zr(eta(2)-CH=NBu(t))}(2)(mu-K)(2)] (9)), and eta(2)-iminoacetyl ([{eta(5):eta(1):eta(1):eta(1)-Et(8)N(4))Zr(eta(2),C(Me)=NBUt)}{Li(THF)}] (10)), complexes. As such, 9 and 10 should be considered as polar alkali-metal iminoformyl and iminoacetyl derivatives bonded to the bifunctional complex 1.

  DOI：

  10.1021/om00010a050