(2,3,7,8,12,13,17,18-octaethylporphyrinato)oxotitanium(IV) | 25087-66-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (2,3,7,8,12,13,17,18-octaethylporphyrinato)oxotitanium(IV)
• 英文别名: (octaethylporphyrinato)titanium(IV) oxide；oxotitanium(IV) octaethylporphinato
• CAS: 25087-66-5
• 化学式: C₃₆H₄₄N₄OTi
• 分子量: 596.652
• InChiKey: LCZRCJVCXTXHOX-YAJYDHHFSA-N

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：

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

  Woo, L. Keith; Hays, J. Alan; Goll, James G., Inorganic Chemistry, 1990, vol. 29, # 20, p. 3916 - 3917

  摘要：

  DOI：
• 作为产物：
  描述：

  Ti(octaethylporphinato)(SO4)*toluene 在 air 作用下， 以 neat (no solvent) 为溶剂， 生成 (2,3,7,8,12,13,17,18-octaethylporphyrinato)oxotitanium(IV)
  参考文献：
  名称：

  Miksztal, Andrew R.; Valentine, Joan Selverstone, Inorganic Chemistry, 1984, vol. 23, # 22, p. 3548 - 3552

  摘要：

  DOI：

文献信息

• Halogenated oxo- and peroxotitanium porphyrinates as sensitizers for the photooxygenation of olefinic compounds
  作者：P Esser

  DOI：10.1016/s1381-1169(98)00213-1

  日期：1999.3.19

  A series of porphines, oxotitanium(IV) and peroxotitanium(IV) porphyrinates were tested as photosensitizers of the singlet oxygen ene reaction with cyclohexene and cis-cyclooctene. The relative order of activity is: H-2(P) > O=Ti(P) greater than or equal to Ti(O-2)P. Best stability is obtained for porphines or porphyrinate complexes with fluorine substituents. Oxotitanium(IV) porphyrinates are active in the decomposition of allylic hydroperoxides. The (photo)catalytic epoxidation occurs less readily than the thermal reaction at 82 degrees C. Attempts of photocatalytic hydrogen peroxide activations lead to fast destruction of O=Ti(P). (C) 1999 Elsevier Science B.V. All rights reserved.
• Intermetal Oxygen Atom Transfer Reactions of Titanium Porphyrins:  Complete vs Incomplete Atom Transfer. X-ray Structure of (μ-Oxo)bis[(<i>meso</i>-tetra-<i>p</i>-tolylporphyrinato)titanium(III)]
  作者：J. Alan Hays、Catherine L. Day、Victor G. Young、L. Keith Woo

  DOI：10.1021/ic960863m

  日期：1996.1.1

  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.