Cationic Cyclopentadienyl Phenylenediamido Titanium Species Generated by Reaction of TiCpR[1,2-C6H4(NCH2t-Bu)2]R (CpR = ![]()
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- 作者：Vanessa Tabernero ; M Carmen Maestre ; Gerardo Jimé ; nez ; Tomá ; s Cuenca ; and Carmen Ramí ; rez de Arellano
- 刊名：Organometallics
- 出版年：2006
- 出版时间：March 27, 2006
- 年：2006
- 卷：25
- 期：7
- 页码：1723 - 1727
- 全文大小：130K
- 年卷期：v.25,no.7(March 27, 2006)
- ISSN：1520-6041
文摘
The reaction of TiCpR[1,2-C6H4(NNp)2]R with the Lewis acid B(C6F5)3 in noncoordinating solventaffords the new zwitterionic species TiCpR[1,2-C6H4(NNp)2)][
-RB(C6F5)3]. When the reaction isperformed in dichloromethane, the [-RB(C6F5)3]- anion is displaced by solvent molecules, giving ionicproducts in which the anion is not coordinated. The cyclopentadienyl zwitterionic complexes TiCp[1,2-C6H4(NNp)2)[-RB(C6F5)3] decompose via ligand scrambling between boron and titanium to give theneutral titanium complex TiCp[1,2-C6H4(NNp)2](C6F5) along with the byproduct RB(C6F5)2. In contrast,the pentamethylcyclopentadienyl analogues TiCp*[1,2-C6H4(NNp)2][-RB(C6F5)3] evolve through C-Hactivation to yield an unresolved mixture of compounds. The molecular structure of TiCp*[1,2-C6H4(NNp)2][-MeB(C6F5)3] has been determined by X-ray diffraction methods.
-RB(C6F5)3]. When the reaction isperformed in dichloromethane, the [-RB(C6F5)3]- anion is displaced by solvent molecules, giving ionicproducts in which the anion is not coordinated. The cyclopentadienyl zwitterionic complexes TiCp[1,2-C6H4(NNp)2)[-RB(C6F5)3] decompose via ligand scrambling between boron and titanium to give theneutral titanium complex TiCp[1,2-C6H4(NNp)2](C6F5) along with the byproduct RB(C6F5)2. In contrast,the pentamethylcyclopentadienyl analogues TiCp*[1,2-C6H4(NNp)2][-RB(C6F5)3] evolve through C-Hactivation to yield an unresolved mixture of compounds. The molecular structure of TiCp*[1,2-C6H4(NNp)2][-MeB(C6F5)3] has been determined by X-ray diffraction methods.