The reaction of the complexes [Ti(η⁵-C₅H₃R′SiMe₂Cl)Cl₃] (R′ = H, SiMe₃) with the terpenoid preligand C₇H₆Me₃(OH)(NCH₂CH₂NH₂) affords the stereospecific synthesis of the constrained-geometry chiral titanium complexes [Ti{(η⁵-C₅H₃R′SiMe₂N(CH₂)₂NC₇H₆Me₃O)-κ³N,N′,O}Cl] (R′ = H, 1; R′ = SiMe₃2), bearing a new cyclopentadienyl-terpenoid ligand derived from α-pinene. The corresponding alkyl derivatives [Ti{(η⁵-C₅H₄SiMe₂N(CH₂)₂NC₇H₆Me₃O)-κ³N,N′,O}R] (R = Me, 4; R = ⁿBu, 5) have been prepared by treatment with suitable alkylating reagents. The reactivity of the methyl complex 4 with different protonic reagents such as alcohols and thiols proceeds via protonation of the amido nitrogen to stereospecifically give the corresponding strain-free alkoxide- and thiolate-methyl compounds [Ti{(η⁵-C₅H₄SiMe₂NH(CH₂)₂NC₇H₆Me₃O)-κO}Me(XR)] (X = O, R = ⁱPr, 6; X = S, R = Et, 7; R = p-MeC₆H₄, 8). The reversibility of this protonation reaction is observed in the case of the thiolate compounds, which are thermically converted, via methane release, into the corresponding constrained-geometry thiolate derivatives [Ti{(η⁵-C₅H₄SiMe₂N(CH₂)₂NC₇H₆Me₃O)-κ³N,N′,O}(SR)] (R = Et, 9; R = C₆H₄-p-Me, 10). However, the analogous alkoxide-methyl compound 6 does not undergo a similar transformation. To gain further insights into the results reached in the reactions of 4 with alcohols and thiols and to understand the different behavior of the strain-free alkoxide- and thiolate-methyl complexes with regard to the thermal decomposition, calculations using DFT methods have been performed.

中文翻译：

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带有α-蒎烯双官能化环戊二烯基萜类配体的手性钛配合物的立体有择合成

配合物[Ti(η ⁵ -C ₅ H ₃ R'SiMe ₂ Cl)Cl ₃ ] (R' = H, SiMe ₃ )与萜类前配体C ₇ H ₆ Me ₃ (OH)(NCH ₂ CH)的反应₂ NH ₂ ) 提供了受限几何手性钛配合物 [Ti{(η ⁵ -C ₅ H ₃ R'SiMe ₂ N(CH ₂ ) ₂ NC ₇ H ₆ Me ₃ O)- κ ³ N的立体定向合成, N' , O }Cl] (R' = H, 1 ; R' = SiMe ₃ 2 )，带有衍生自 α-蒎烯的新的环戊二烯基萜类配体。相应的烷基衍生物[Ti{(η ⁵ -C ₅ H ₄ SiMe ₂ N(CH ₂ ) ₂ NC ₇ H ₆ Me ₃ O) -κ ³ N , N ', O }R] (R = Me, 4 ; R = ⁿ Bu, 5) 是通过用合适的烷基化试剂处理而制备的。甲基配合物4与醇和硫醇等不同质子试剂的反应性通过酰氨基氮的质子化进行，立体定向地得到相应的无应变醇盐和硫醇盐甲基化合物 [Ti{(η ⁵ -C ₅ H ₄ SiMe ₂ NH(CH ₂ ) ₂ NC ₇ H ₆ Me ₃ O) -κO }Me(XR)] (X = O, R = ⁱ Pr, 6 ; X = S, R = Et, 7 ; R = p -MeC ₆小时₄, 8 )。在硫醇化合物的情况下观察到这种质子化反应的可逆性，这些化合物通过甲烷释放热转化为相应的受限几何硫醇衍生物 [Ti{(η ⁵ -C ₅ H ₄ SiMe ₂ N(CH ₂ ) ₂ NC ₇ H ₆ Me ₃ O) -κ ³ N , N ', O }(SR)] (R = Et, 9 ; R = C ₆ H ₄ - p -Me, 10 )。然而，类似的醇盐-甲基化合物6没有经历类似的转变。为了进一步了解4与醇和硫醇的反应结果，并了解无应变的醇盐和硫醇盐甲基配合物在热分解方面的不同行为，使用 DFT 方法进行了计算。