bis(μchloro)dichloro(methylbenzoate)isopropoxotitanium(IV) | 174686-88-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(μchloro)dichloro(methylbenzoate)isopropoxotitanium(IV)
• 英文别名: methyl benzoate;propan-2-olate;trichlorotitanium(1+)
• CAS: 174686-88-5
• 化学式: C₂₂H₃₀Cl₆O₆Ti₂
• 分子量: 698.955
• InChiKey: MYYMEYUOUBTVBR-UHFFFAOYSA-H

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：

  苯甲酸甲酯 、 Ti(OiPr)Cl3 以 甲苯 为溶剂， 生成 bis(μchloro)dichloro(methylbenzoate)isopropoxotitanium(IV)
  参考文献：
  名称：

  Chemistry of Ti(OⁱPr)Cl₃ with Chloride and Oxygen-Containing Ligands:  The Roles of Alkoxide and Solvents in the Six-Coordinate Titanium Complexes

  摘要：

  Ti((OPr)-Pr-i)Cl-3 reacts easily with various ligands to form a series of six-coordinate complexes, [Ti((OPr)-Pr-i)Cl-5](2-)(HAm+)(2) (Am = NEt(3) (7a) or NC5H5 (7b)), Ti((OPr)-Pr-i)Cl(3)L(2) (L = THF (8) or PhCHO (9)), Ti((OPr)-Pr-i)-Cl-3(PhCHO)(Et(2)O) (10), and [Ti((OPr)-Pr-i)Cl-2(mu-Cl)(PhC(O)OMe)](2) (11). Upon dissolution of 7a in THF, 8 was obtained. When 1 mol equiv of HNEt(3)Cl was added to 8, [Ti((OPr)-Pr-i)Cl-4(THF)](-)(HNEt(3))+ (12) was obtained. With the addition of another 1 mol equiv of HNEt(3)Cl, 12 was converted to 7a. One THF in 8 can be removed in vacuo to give the chloride-bridged dimer [Ti((OPr)-Pr-i)Cl-2(mu-Cl)(THF)](2) (13) which can be converted back to 8 by dissolving in THF. 13 was found to react with 2 mol equiv of HNEt(3)Cl or PhCHO to give 12 and Ti((OPr)-Pr-i)Cl-3(PhCHO)(THF) (14), respectively. The molecular structures of 7b, 8, and 10-13 show short Ti-(OPr)-Pr-i distances, and the relative bonding order of (OPr)-O---Pr-i > Cl-, THF > Et(2)O > PhCHO > mu-Cl- > RC(O)OMe is discussed based on the solid state structures. This bonding sequence is very useful for the prediction of the geometry for six-coordinate complexes of early transition metals with the following principle: The strongest ligand prefers a trans position to the weakest ligand, and the second strongest ligand favors a trans position to the second weakest ligand in the complex. Kinetically, the trans position to the isopropoxide is rather labile for substitution, and the lability of the trans ligand ensures the effectiveness of titanium alkoxides for subsequent reactions or as catalysts in many asymmetric organic syntheses.

  DOI：

  10.1021/ja952730q