922161-35-1Relevant academic research and scientific papers
Alkylation, cation formation, and insertion reactions in titanium tris(ketimide) complexes
Ferreira, M. Joao,Matos, Ines,Ascenso, Jose R.,Duarle, M. Teresa,Marques, M. Merces,Wilson, Claire,Martins, Ana M.
, p. 119 - 127 (2008/10/09)
Ti(N=CtBu2)3Cl (1) reacts with TlPF 6 in acetonitrile to afford [Ti(N=CtBu2) 3(N≡CCH3)]PF6 (2), which proved to be unstable and decomposed at room temperature either in solution or in the solid state. Attempts to recrystallize 2 from a CH2Cl2/hexane mixture led to [Ti3(N=CtBu2) 6(μ2-F)3(μ3-F) 2][PF6 (3). Treatment of 1 with LiMe and PhCH 2MgCl gave the compounds Ti(N=CtBu2) 3CH2Ph (4) and Ti(N=CtBu2) 3Me (5), respectively. 4 was treated with B(C6F 5)3 to afford [Ti(N=CtBu2) 3(CH2Ph)B(C6F5)3] (6), which exists in solution as a mixture of two species, the zwitterion [Ti(N=CtBu2)3][(μ-CH2Ph)B(C 6F5)3] (6A) and the solvate cation [Ti(N=C tBu2)3(Solv)][(CH2Ph)B(C 6F5)3] (6B). Above 60 °C, C 6F5 is transferred to the metal center and Ti(N=C tBu2)3(C6F5) (9) forms. This compound participates in a dynamic process in solution involving Ti...F interactions. The fluxional process observed for 6 can be stopped upon addition of 1 equiv of C≡NMes, giving [Ti(N=CtBu 2)3(C=NMes)][(CH2Ph)B(C6F 5)3] (7). C≡NMes does not insert into Ti-N bonds, but it readily inserts into the Ti-C bond of Ti(N=CtBu 2)3(Me) (5) to afford [Ti(N=CtBu 2)3{η2-C(CH3)=NMes}] (8).
