Synthesis, Structural Features, and Formation of Organometallic Derivates of C1-Bridged Cp/Amido Titanium and Zirconium “CpCN-Constrained Geometry” Systems

A series of C1-bridged Cp/amido group 4 metal complexes [(“CpCN”)MX2] was prepared. The starting compound 6-tert-butylfulvene (7) was reacted with LiNHR (R = o-anisyl (a), p-anisyl (b), phenyl (c), or tert-butyl (d)) to yield the Li(C5H4-CH(tBu)-NHR) compounds (8). Subsequent deprotonation with n-butyllithium, followed by transmetalation with Cl2Ti(NMe2)2, yielded the (“CpCN”)Ti(NR2)2 complexes 10 (ad). A second synthetic series started from 6-(dimethylamino)fulvene (11). The reaction with the LiNHR reagents led to addition followed by HNMe2 elimination to yield the respective imino-substituted cyclopentadienides Li(C5H4-CHNR) (13). Addition of methyllithium to 13 gave the (Li+)2(C5H4-CHMe-NR)2-, (“CpCN”)2-, ligands (14). Transmetalation with Cl2Ti(NMe2)2 subsequently yielded the corresponding μ-CHMe-bridged Cp/amido group 4 complexes 15 (ac). Treatment with Me2SiCl2 cleanly converted the (“CpCN”)M(NR2)2 complexes to the respective (“CpCN”)MCl2 systems [3ad, 4ac (Ti), 5a (Zr)]. These were transformed to the (“CpCN”)M(CH3)2 complexes [μ-CHCMe3:  17ad (Ti), 19a (Zr), μ-CHMe:  18ac (Ti)] and the (s-cis-supine-η4-butadiene)(“CpCN”)Ti systems 21ad and 22b,c. With respect to X-ray structure analyses the (CpCN)MX2 systems must be regarded as more “constrained” than their (“CpSiN”)MX2 analogues. The (“CpCN”)MCl2 and (“CpCN”)M(CH3)2 complexes were used as catalysts for ethene homopolymerization and ethene/1-octene copolymerization. All systems gave active catalysts, but these were quite different in their catalytic performance when compared with the usually applied (“CpSiN”)TiX2-derived catalysts. The (“CpCN”)M catalyst activities and selectivities were very dependent on the specific activator components employed.