Tri- and Tetravalent Titanium Alkyls Supported by Organic Amides
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- 作者：Ravinder K. Minhas ; Ludmila Scoles ; Shirley Wong ; and Sandro Gambarotta
- 刊名：Organometallics
- 出版年：1996
- 出版时间：February 20, 1996
- 年：1996
- 卷：15
- 期：4
- 页码：1113 - 1121
- 全文大小：533K
- 年卷期：v.15,no.4(February 20, 1996)
- ISSN：1520-6041
文摘
The reactions of both trivalent[(Cy2N)2Ti(
-Cl)2Li(TMEDA)](1) and tetravalent[(Cy2N)2TiCl2] (5) with R'Li in THF or diethyl ethergave Ti(IV) complexes(Cy2N)2TiR'2 [R' =CH2CMe3 (7),CH2CMe2Ph (8),CH2SiMe3 (9)].Conversely, the reactions of 1,[{(i-Pr)2N}2TiCl2][Li(TMEDA)2](2), and[{(Me3Si)2N}2TiCl2][Li(TMEDA)2](3) with R'Li [R' = Me,Ph, CH2Ph] gave the corresponding trivalentderivatives[(Cy2N)2Ti(-Bz)2Li(TMEDA)](4a),[(Cy2N)2Ti(-Me)2Li(TMEDA)](4b),[{(i-Pr)2N}2TiPh2][Li(TMEDA)2](11), and[{(Me3Si)2N}2Ti(CH2Ph)2][Li(TMEDA)2](12) via simple ligand replacement reactions.Oxidation of 12 withdiphenylfulvene gave{(Me3Si)2N}2Ti(CH2Ph)2(13). All these compounds are thermallylabileand yielded intractable materials upon thermolysis. Only in thecase of the neophylderivative(Cy2N)2Ti(CH2CMe2C6H5)2(8) a cyclometalated compound(Cy2N)2Ti(CH2CMe2C6H4) (10) wasisolated and crystallized from the thermolyzed solution. Thereactionof 1 with styrene oxide provided the Ti-oxo complex[(Cy2N)2TiCl]2O(14) which gave, uponalkylation with MeLi, the corresponding dinuclear alkyl derivatives[(Cy2N)2TiMe]2O(15).The molecular structures of 1 and 10-14were demonstrated by X-ray diffraction analysis.
-Cl)2Li(TMEDA)](1) and tetravalent[(Cy2N)2TiCl2] (5) with R'Li in THF or diethyl ethergave Ti(IV) complexes(Cy2N)2TiR'2 [R' =CH2CMe3 (7),CH2CMe2Ph (8),CH2SiMe3 (9)].Conversely, the reactions of 1,[{(i-Pr)2N}2TiCl2][Li(TMEDA)2](2), and[{(Me3Si)2N}2TiCl2][Li(TMEDA)2](3) with R'Li [R' = Me,Ph, CH2Ph] gave the corresponding trivalentderivatives[(Cy2N)2Ti(-Bz)2Li(TMEDA)](4a),[(Cy2N)2Ti(-Me)2Li(TMEDA)](4b),[{(i-Pr)2N}2TiPh2][Li(TMEDA)2](11), and[{(Me3Si)2N}2Ti(CH2Ph)2][Li(TMEDA)2](12) via simple ligand replacement reactions.Oxidation of 12 withdiphenylfulvene gave{(Me3Si)2N}2Ti(CH2Ph)2(13). All these compounds are thermallylabileand yielded intractable materials upon thermolysis. Only in thecase of the neophylderivative(Cy2N)2Ti(CH2CMe2C6H5)2(8) a cyclometalated compound(Cy2N)2Ti(CH2CMe2C6H4) (10) wasisolated and crystallized from the thermolyzed solution. Thereactionof 1 with styrene oxide provided the Ti-oxo complex[(Cy2N)2TiCl]2O(14) which gave, uponalkylation with MeLi, the corresponding dinuclear alkyl derivatives[(Cy2N)2TiMe]2O(15).The molecular structures of 1 and 10-14were demonstrated by X-ray diffraction analysis.