(octaethylporphyrinato)titanium(IV) dichloride | 123622-94-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (octaethylporphyrinato)titanium(IV) dichloride
• 英文别名: {(OEP)TiCl2}
• CAS: 123622-94-6
• 化学式: C₃₆H₄₄Cl₂N₄Ti
• 分子量: 651.558
• InChiKey: UGPKGJLNQWPDKC-PALJMRDHSA-L

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：

  (octaethylporphyrinato)titanium(IV) dichloride 、 二苯基乙炔 在 lithium aluminum hydride 作用下， 以 甲苯 为溶剂， 以51%的产率得到(η2-diphenylacetylene)titanium octaethylporphyrin
  参考文献：
  名称：

  Woo, L. Keith; Hays, J. Alan; Jacobson, Robert A., Organometallics, 1991, vol. 10, # 7, p. 2102 - 2104

  摘要：

  DOI：
• 作为产物：
  描述：

  (2,3,7,8,12,13,17,18-octaethylporphyrinato)oxotitanium(IV) 、 [Ti(meso-tetra-p-tolylporphyrin)Cl2] 以 氯仿 为溶剂， 生成 (octaethylporphyrinato)titanium(IV) dichloride 、 oxotitanium(IV) meso-tetrakis(4-methylphenyl)porphinato
  参考文献：
  名称：

  Intermetal Oxygen Atom Transfer Reactions of Titanium Porphyrins:  Complete vs Incomplete Atom Transfer. X-ray Structure of (μ-Oxo)bis[(meso-tetra-p-tolylporphyrinato)titanium(III)]

  摘要：

  Treatment of (meso-tetra-p-tolylporphyrinato)titanium(IV) oxide, (TTP)Ti=O, with (octaethylporphyrinato)titanium(III)chloride, (OEP)Ti-Cl, in toluene-d(8) results in the reversible exchange of axial ligands to form (TTP)Ti-Cl and (OEP)Ti=O. The net result is a formal one-electron redox process. This occurs with a second-order rate constant of (2.4 +/- 0.2) x 10(2) M(-1) s(-1) to form an equilibrium mixture with K = 1.7 +/- 0.4 at 20 degrees C (Delta H double dagger = 10.8 +/- 0.4 kcal/mol, Delta S double dagger = -10.7 +/- 1.2 cal/mol . K). Use of pivalate in place of chloride on the Ti(III) complex causes no significant change in the rate of this one-electron redox process. In addition, excess chloride only partially inhibits the rate of oxygen transfer with chlorotitanium(III) complexes. A complete kinetic analysis indicates that these redox processes proceed through two parallel pathways, both involving an inner sphere mu-oxo intermediate. Competing associative and dissociative (chloride or pivalate loss) mechanisms are in effect. Reversible oxo/chloro exchange also occurs between (TTP)TiCl2 and (OEP)Ti=O in CHCl3 to produce (TTP)Ti=O and (OEP)TiCl2 with K = 47 +/- 13 and k(f) = 5 +/- 1 M(-1)s(-1) at 20 degrees C (Delta H double dagger = 11 +/- 1 kcal/mol, Delta S double dagger = 11 +/- 3 cal/mol . K, Delta H degrees = -3.7 +/- 0.8 kcal/mol, and Delta S degrees = -5 +/- 2 cal/mol . K). In contrast, when (TTP)Ti=O is treated with (TPP)Ti(eta(2)-PhC=CPh), incomplete oxygen atom transfer occurs to produce the mu-oxo complex, [(TTP)Ti]O-2. X-ray quality crystals of this complex can be prepared by the slow diffusion of O-2 into a solution of (TTP)Ti(4-picoline)(2). The structure of the mu-oxo complex, C114H90N8OTi2, was determined by single-crystal X-ray diffraction (crystal data: monoclinic, C2/c, a = 32.044(8) Angstrom, b = 16.908(5) Angstrom, c = 18.525(5) Angstrom, beta = 117.91(2)degrees, V = 8869(4) Angstrom(3), Z = 4, R = 5.88%, and R(w) = 15.38%). Key metrical parameters include a Ti-O distance of 1.7941(8) Angstrom, average Ti-N distances of 2.113(3) Angstrom, and a Ti-O-Ti angle of 170.8(2)degrees. The Ti atom is displaced 0.66 Angstrom out of the mean porphyrin plane toward the oxo bridge.

  DOI：

  10.1021/ic960863m