Alkylation, Cation Formation, and Insertion Reactions in Titanium Tris(ketimide) Complexes
详细信息 查看全文
- 作者：M. Joã ; o Ferreira ; Inê ; s Matos ; José ; R. Ascenso ; M. Teresa Duarte ; M. Mercê ; s Marques ; Claire Wilson ; Ana M. Martins
- 刊名：Organometallics
- 出版年：2007
- 出版时间：January 1, 2007
- 年：2007
- 卷：26
- 期：1
- 页码：119 - 127
- 全文大小：238K
- 年卷期：v.26,no.1(January 1, 2007)
- ISSN：1520-6041
文摘
Ti(N=CtBu2)3Cl (1) reacts with TlPF6 in acetonitrile to afford [Ti(N=CtBu2)3(N
tities/tbd1.gif">CCH3)]PF6 (2), whichproved to be unstable and decomposed at room temperature either in solution or in the solid state. Attemptsto recrystallize 2 from a CH2Cl2/hexane mixture led to [Ti3(N=CtBu2)6(tities/mgr.gif">2-F)3(tities/mgr.gif">3-F)2][PF6] (3). Treatmentof 1 with LiMe and PhCH2MgCl gave the compounds Ti(N=CtBu2)3CH2Ph (4) and Ti(N=CtBu2)3Me(5), respectively. 4 was treated with B(C6F5)3 to afford [Ti(N=CtBu2)3(CH2Ph)B(C6F5)3] (6), which existsin solution as a mixture of two species, the zwitterion [Ti(N=CtBu2)3][(tities/mgr.gif">-CH2Ph)B(C6F5)3] (6A) and thesolvate cation [Ti(N=CtBu2)3(Solv)][(CH2Ph)B(C6F5)3] (6B). Above 60 tities/deg.gif">C, C6F5 is transferred to themetal center and Ti(N=CtBu2)3(C6F5) (9) forms. This compound participates in a dynamic process insolution involving Ti···F interactions. The fluxional process observed for 6 can be stopped upon additionof 1 equiv of Ctities/tbd1.gif">NMes, giving [Ti(N=CtBu2)3(Ctities/tbd1.gif">NMes)][(CH2Ph)B(C6F5)3] (7). Ctities/tbd1.gif">NMes does notinsert into Ti-N bonds, but it readily inserts into the Ti-C bond of Ti(N=CtBu2)3(Me) (5) to afford[Ti(N=CtBu2)3{
ta.gif" BORDER=0 >2-C(CH3)=NMes}] (8).
tities/tbd1.gif">CCH3)]PF6 (2), whichproved to be unstable and decomposed at room temperature either in solution or in the solid state. Attemptsto recrystallize 2 from a CH2Cl2/hexane mixture led to [Ti3(N=CtBu2)6(tities/mgr.gif">2-F)3(tities/mgr.gif">3-F)2][PF6] (3). Treatmentof 1 with LiMe and PhCH2MgCl gave the compounds Ti(N=CtBu2)3CH2Ph (4) and Ti(N=CtBu2)3Me(5), respectively. 4 was treated with B(C6F5)3 to afford [Ti(N=CtBu2)3(CH2Ph)B(C6F5)3] (6), which existsin solution as a mixture of two species, the zwitterion [Ti(N=CtBu2)3][(tities/mgr.gif">-CH2Ph)B(C6F5)3] (6A) and thesolvate cation [Ti(N=CtBu2)3(Solv)][(CH2Ph)B(C6F5)3] (6B). Above 60 tities/deg.gif">C, C6F5 is transferred to themetal center and Ti(N=CtBu2)3(C6F5) (9) forms. This compound participates in a dynamic process insolution involving Ti···F interactions. The fluxional process observed for 6 can be stopped upon additionof 1 equiv of Ctities/tbd1.gif">NMes, giving [Ti(N=CtBu2)3(Ctities/tbd1.gif">NMes)][(CH2Ph)B(C6F5)3] (7). Ctities/tbd1.gif">NMes does notinsert into Ti-N bonds, but it readily inserts into the Ti-C bond of Ti(N=CtBu2)3(Me) (5) to afford[Ti(N=CtBu2)3{ta.gif" BORDER=0 >2-C(CH3)=NMes}] (8).