[Ti(meso-tetra-p-tolylporphyrin)Cl2] | 129679-91-0

• 英文名称: [Ti(meso-tetra-p-tolylporphyrin)Cl2]
• 英文别名: (meso-tetra-p-tolylporphyrinato)titanium(IV) dichloride；(5,10,15,20-tetra-p-tolylporphyrinato)dichlorotitanium；(meso-5,10,15,20-tetra-p-tolylporphyrinato)TiCl2；(meso-tetra-p-tolylporphyrinato)TiCl2
• CAS: 129679-91-0
• 化学式: C₄₈H₃₆Cl₂N₄Ti
• 分子量: 787.627
• InChiKey: MXXLUCANWVCPHP-KDTBAHQYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• 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：

  [Ti(meso-tetra-p-tolylporphyrin)Cl2] 以 甲苯 为溶剂， 生成 (meso-5,10,15,20-tetra-p-tolylporphyrinato)Ti(OPh)2
  参考文献：
  名称：

  Gray, Steven D.; Thorman, Joseph L.; Berreau, Lisa M., Inorganic Chemistry, 1997, vol. 36, # 3, p. 278 - 283

  摘要：

  DOI：
• 作为产物：
  描述：

  tetrachlorobis(tetrahydrofuran)titanium(IV) 、 5,10,15,20-tetra-p-tolylporphyrin, dilithium salt * 2 THF 以 甲苯 为溶剂， 以60%的产率得到[Ti(meso-tetra-p-tolylporphyrin)Cl2]
  参考文献：
  名称：

  Berreau, Lisa M.; Hays, J. Alan; Young Jr., Victor G., Inorganic Chemistry, 1994, vol. 33, # 1, p. 105 - 108

  摘要：

  DOI：

文献信息

• Synthesis, Characterization, and Reactivity of Group 4 Metalloporphyrin Diolate Complexes
  作者：Guodong Du、L. Keith Woo

  DOI：10.1021/om020790g

  日期：2003.2.1

  A number of group 4 metalloporphyrin diolate complexes were synthesized via various approaches. For example, treatment of imido complex (TTP)HfNAriPr with diols resulted in formation of the corresponding diolato complexes (TTP)Hf[OCR1R2CR1R2O] (R1 = R2 = Me, 1; R1 = Me, R2 = Ph, 2; R1 = R2 = Ph, 3). Treatment of (TTP)TiNiPr with diols generated (TTP)Ti[OCR1R2CR1R2O] (R1 = R2 = Me, 5; R1 = Me, R2 =

  通过各种方法合成了许多第4族金属卟啉二醇酸酯复合物。例如，用二醇处理亚胺基络合物（TTP）Hf NAr iPr导致形成相应的二醇基络合物（TTP）Hf [OCR 1 R 2 CR 1 R 2 O]（R 1 = R 2 = Me，1 ; R 1 = Me，R 2 = Ph，2； R 1 = R 2 = Ph，3）。用生成的二醇（TTP）Ti [OCR 1 R 2 CR 1处理（TTP）Ti N i PrR 2 O]（R 1＝ R 2＝ Me，5； R 1＝ Me，R 2＝ Ph，6； R 1＝ H，R 2＝ Ph，7； R 1＝ H，R 2＝对甲苯基，8）。或者，通过（TTP）MCl 2（M = Hf，Ti）与松果酸二钠的复分解反应制备pin酸钛和pin酸钛1和5。complex配合物的取代化学与二醇基配体的碱性密切相关。配合1 - 6进行氧化裂解反应，生成羰基化合物和金属氧卟啉。对于较少取
• Synthesis and Reactivity of Hydrazido(2-) and Imido Derivatives of Titanium(IV) Tetratolylporphyrin
  作者：Joseph L. Thorman、L. Keith Woo

  DOI：10.1021/ic990991l

  日期：2000.3.1

  Titanium porphyrin hydrazido complexes (TTP)Ti = NNR2 (TTP = meso-tetra-p-tolylporphyrinato dianion; R = Me (1), Ph (2)) were synthesized by treatment of (TTP)TiCl2 with 1,1-disubstituted hydrazines H2NNR2 (R = Me, Ph) in the presence of piperdine. The nucleophilic character of the hydrazido moiety was demonstrated in the reactions of complexes 1 and 2 with p-chlorobenzaldehyde, which yielded the titanium

  钛卟啉肼基络合物（TTP）Ti = NNR2（TTP =中-四-对-甲苯基卟啉二阴离子; R = Me（1），Ph（2））是通过用1,1-二取代肼处理（TTP）TiCl2合成的在哌啶存在下，H2NNR2（R = Me，Ph）。在配合物1和2与对氯苯甲醛的反应中证实了肼基部分的亲核特性，这产生了钛氧代配合物（TTP）-Ti ＝ O和相应的。配合物1和2用苯酚或水的质子化分别生成1,1,2-取代的肼和（TTP）Ti（OPh）2或（TTP）Ti =O。观察到对氯苯甲醛和苯酚与（TTP）Ti = NiPr，3具有相似的反应性。配合物3与亚硝基苯的反应干净地形成了偶氮化合物iPrN = NPh和末端氧代产物（TTP）Ti = O.
• 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.
• Woo, L. Keith; Hays, J. Alan; Goll, James G., Inorganic Chemistry, 1990, vol. 29, # 20, p. 3916 - 3917
  作者：Woo, L. Keith、Hays, J. Alan、Goll, James G.

  DOI：——

  日期：——
• Woo, L. Keith; Hays, J. Alan; Young Jr., Victor G., Inorganic Chemistry, 1993, vol. 32, # 20, p. 4186 - 4192
  作者：Woo, L. Keith、Hays, J. Alan、Young Jr., Victor G.、Day, Catherine L.、Caron, Cecile、D'Souza, Francis、Kadish, Karl M.

  DOI：——

  日期：——