Cyclopentadienyl-Amido Ligands with a Pendant "-NHR" Amino Functionality in Titanium Chemistry. Molecular Structure of [Ti{5
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- 作者：Gerardo Jimé ; nez ; Pascual Royo ; Tomá ; s Cuenca ; and Eberhardt Herdtweck
- 刊名：Organometallics
- 出版年：2002
- 出版时间：May 27, 2002
- 年：2002
- 卷：21
- 期：11
- 页码：2189 - 2195
- 全文大小：106K
- 年卷期：v.21,no.11(May 27, 2002)
- ISSN：1520-6041
文摘
The reaction of the chlorodimethylsilyl-substituted cyclopentadienyl titanium compound[Ti(
5-C5H4SiMe2Cl)Cl3] (1) with 1 equiv of NH2(CH2)2NHR (R = H, CHMe2), in the presenceof 2 equiv of NEt3, afforded the mononuclear complexes [Ti{5-C5H4SiMe2--N(CH2)2--NHR}Cl2] (R = H, 2; CHMe2, 3) in high yield. While 2 is stable in solution, 3 slowly evolves intothe strain-free complex [Ti{5-C5H4SiMe2NH(CH2)2--NCHMe2}Cl2] (4). 1 reacts with 0.5equiv of ethylenediamine to yield a mixture of 2 and the dinuclear titanium complex [Ti{5-C5H4SiMe2--N(CH2)-}Cl2]2 (5), which contains two tethered cyclopentadienyl-silyl-amidofragments. Compound 5 is also obtained from the reaction of 2 with 1. Treatment of 1 with0.5 equiv of propylenediamine rendered the dinuclear compound [Ti{5-C5H4SiMe2--N(CH2)1.5-}Cl2]2 (6), whereas a mixture of 6 and the mononuclear species [Ti{5-C5H4SiMe2--N(CH2)3NH2}Cl2] (7) was spectroscopically observed when 1 was reacted with 1 equiv ofNH2(CH2)3NH2 in C6D6. A similar reaction of 1 with N-methylpropylenediamine regioselectively affords the unstrained mononuclear compound [Ti{5-C5H4SiMe2NH(CH2)3--NMe}Cl2] (8). Dinuclear derivatives [Ti{5-C5H4SiMe2--N(CH2)x-}Cl2]2 (x = 2 (9); 2.5 (10)) wereprepared by reacting complex 1 with butylenediamine and pentylenediamine, respectively.These compounds were characterized by elemental analysis and NMR spectroscopy. Thecrystal structure of 3 was determined by X-ray diffraction methods.
5-C5H4SiMe2Cl)Cl3] (1) with 1 equiv of NH2(CH2)2NHR (R = H, CHMe2), in the presenceof 2 equiv of NEt3, afforded the mononuclear complexes [Ti{5-C5H4SiMe2--N(CH2)2--NHR}Cl2] (R = H, 2; CHMe2, 3) in high yield. While 2 is stable in solution, 3 slowly evolves intothe strain-free complex [Ti{5-C5H4SiMe2NH(CH2)2--NCHMe2}Cl2] (4). 1 reacts with 0.5equiv of ethylenediamine to yield a mixture of 2 and the dinuclear titanium complex [Ti{5-C5H4SiMe2--N(CH2)-}Cl2]2 (5), which contains two tethered cyclopentadienyl-silyl-amidofragments. Compound 5 is also obtained from the reaction of 2 with 1. Treatment of 1 with0.5 equiv of propylenediamine rendered the dinuclear compound [Ti{5-C5H4SiMe2--N(CH2)1.5-}Cl2]2 (6), whereas a mixture of 6 and the mononuclear species [Ti{5-C5H4SiMe2--N(CH2)3NH2}Cl2] (7) was spectroscopically observed when 1 was reacted with 1 equiv ofNH2(CH2)3NH2 in C6D6. A similar reaction of 1 with N-methylpropylenediamine regioselectively affords the unstrained mononuclear compound [Ti{5-C5H4SiMe2NH(CH2)3--NMe}Cl2] (8). Dinuclear derivatives [Ti{5-C5H4SiMe2--N(CH2)x-}Cl2]2 (x = 2 (9); 2.5 (10)) wereprepared by reacting complex 1 with butylenediamine and pentylenediamine, respectively.These compounds were characterized by elemental analysis and NMR spectroscopy. Thecrystal structure of 3 was determined by X-ray diffraction methods.