[thallium(III) (tetraphenylporphyrinato-N-O) (acetate)]*(dichloromethane) | 907996-76-3

• 英文名称: [thallium(III) (tetraphenylporphyrinato-N-O) (acetate)]*(dichloromethane)
• 英文别名: [Tl(tpp-N-O)(OAc)*CH2Cl2
• CAS: 907996-76-3
• 化学式: CH₂Cl₂*C₄₆H₃₁N₄O₃Tl
• 分子量: 977.093
• InChiKey: GRINBZTUQWNTGM-HGCFFUDKSA-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

• 作为产物：
  描述：

  meso-tetraphenylporphyrin N-oxide 、 二氯甲烷 、 thallium(III) acetate 以 甲醇 、 二氯甲烷 为溶剂， 以70%的产率得到[thallium(III) (tetraphenylporphyrinato-N-O) (acetate)]*(dichloromethane)
  参考文献：
  名称：

  Thallium complexes of tetraphenylporphyrin: Tl(tpp-N-O)(OAc) and cis-acetato-N-p-tert-butylbenzensulfonylimido-meso-tetraphenylporphyrinatothallium(III) Tl(N-p-NSO2C6H4tBu-tpp)(OAc)

  摘要：

  The crystal structures of Tl(tpp-N-O)(OAc) (3) and acetato-N-p-tert-butylbenzensulfonylimido-meso-tetraphenylporphyrinatothallium(III) Tl(N-p-(NSO2C6H4Bu)-Bu-t-tpp)(OAc) (5) have been determined. The coordination sphere around Tl3+ is a distorted square-based pyramid in which the apical site is occupied by a bidentate chelating OAc- group for 3 and 5. The plane of three pyrrole nitrogen atoms (i.e., N(1), N(2) and N(3)), strongly bonded to Tl3+ in 3 and 5, is adopted as a reference plane, 3N. The porphyrin ring is severely distorted and the pyrrole ring N(4) bonding to the oxygen and (NSO2C6H4Bu)-Bu-t group makes a dihedral angle of 46.5 degrees and 46.7 degrees with the 3N plane for 3 and 5, respectively. In 3, Tl3+ and O(1) are located on the same side at 1.11 and 1.34 angstrom from its 3N plane, and in 5, Tl3+ and N(5) are also located on the same side at 1.15 and 1.30 angstrom from its 3N plane. The free energy of activation at the coalescence T-c for the intermolecular acetate exchange process of 3 and 5 in CD2Cl2 is found to be Delta G(184)double dagger = 39.3 and Delta G(208)double dagger = 44.1 kJ/mol, respectively, through H-1 NMR variable temperature measurements.An electronegative substituent, O(1), bonded to Tl in 3 causes a significant negative contribution up to 145 Hz for Delta(3)J(Tl-C, O) and 79 Hz for Delta(2) J(Tl-C, O) for OAc- in 3. (C) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2006.01.020