The reaction of TiCl_4–n(OⁱPr)_n (n = 0, 2, 4) with various terpenoid preligands based on α-pinene, C₇H₆Me₃(OH)(NCH₂CH₂G) (G = NH₂, I; NHMe, II; OH, III), stereoselectively affords a series of new chiral titanium(IV) complexes. Such complexes are either octahedral, [TiCl₂X(OC₇H₆Me₃NCH₂CH₂G-κ³N,N,O)] (X = Cl, G = NH₂, 1; X = OⁱPr, G = NH₂, 2; G = NHMe, 3), or trigonal bipyramidal, [Ti(OⁱPr)₃(OC₇H₆Me₃NCH₂CH₂G-κ²N,O)] (G = NH₂, 4; NHMe, 5) and [TiX(OⁱPr)(OC₇H₆Me₃NCH₂CH₂O-κ³N,O,O*)] (X = Cl, 6; OⁱPr, 8), depending on the acidity of titanium, the reaction conditions and the nature of the pendant ending group of the terpenoid ligand. Density functional theory (DFT) calculations have been carried out to assess the stability of the multiple possible diastereoisomers allowing us to propose structural suggestions. The new titanium complexes efficiently catalyze the selective oxidation of various types of sulfides to either sulfoxides or sulfones using aqueous hydrogen peroxide, under mild conditions. All compounds have been characterized by multinuclear NMR spectroscopy and the molecular structure for some of them has been determined by X-ray diffraction.

中文翻译：

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包含基于α-P烯的多齿配体的手性钛（IV）配合物。过氧化氢硫氧化的催化活性

TiCl _{4– n}（O ⁱ Pr）_n（n = 0、2、4）与各种基于α-，烯，C ₇ H ₆ Me ₃（OH）（NCH ₂ CH ₂ G）（G （NH ₂，I； NHMe，II； OH，III），立体选择性地提供了一系列新的手性钛（IV）配合物。这样的复合物或者是八面体，[的TiCl ₂ X（OC ₇ ħ ₆我₃ NCH ₂ CH ₂ G-κ ³ Ñ，Ñ，Õ）]（X =氯，G = NH ₂，1 ; X = O^我PR，G = NH ₂，2 ; G = NHMe，3），或三角双锥，钛[Ti（O^我PR）₃（ OC ₇ ħ ₆我₃ NCH ₂ CH ₂ G-κ ² ñ，Õ）]（G = NH ₂，4 ; NHMe，5）和[TIX（O^我PR）（OC ₇ ħ ₆我₃ NCH ₂ CH ₂O形κ ³ Ñ，Ô，○*）]（X =氯，6 ;○^我PR，8），取决于钛的酸度，反应条件和萜类配体的侧基末端的性质。已经进行了密度泛函理论（DFT）计算，以评估多种可能的非对映异构体的稳定性，从而使我们能够提出结构建议。在温和的条件下，使用过氧化氢水溶液，新型钛络合物可有效催化各种类型的硫化物选择性氧化为亚砜或砜。所有化合物均已通过多核NMR光谱进行了表征，其中某些化合物的分子结构已通过X射线衍射确定。