Studies Related to the Chloro Titanium and Zirconium Complexes with [η 5 ‐Cyclopentadienyldi(silylamido)] Ligands

Trichloro complexes [M{η 5 ‐C 5 H 3 [SiMe 2 (NH t Bu)] 2 }Cl 3 ] [M = Zr ( 2 ), Ti ( 3 )] have been synthesized by reaction of the corresponding chlorides MCl 4 with the lithium salt LiC 5 H 3 [SiMe 2 (NH t Bu)] 2 ( 1 ). Complexes 2 and 3 react with 2 equiv. of TiCl 4 in toluene at 110°C to afford the di(chlorosilyl) derivatives [M{η 5 ‐C 5 H 3 (SiMe 2 Cl) 2 }Cl 3 ] [M = Ti ( 5 ), Zr ( 8 )]. Intermediate formation of [Ti{η 5 ‐C 5 H 3 [SiMe 2 (NH t Bu)](SiMe 2 Cl)}Cl 3 ] ( 4 ) has been proven by NMR spectroscopy. Reaction of 1 with TiCl 4 (2 equiv.) in toluene at 110 °C in the presence of excess NEt 3 has yielded the chloro‐silyl complex [Ti{η 5 ‐C 5 H 3 (SiMe 2 Cl)(SiMe 2 ‐η 1 ‐N t Bu)}Cl 2 ] ( 7 ) through the intermediate formation of the amino‐silyl derivative [Ti{η 5 ‐C 5 H 3 [SiMe 2 (NH t Bu)] (SiMe 2 ‐η 1 ‐N t Bu)}Cl 2 ] ( 6 ). Reactions of di‐ ansa ‐[M{η 5 ‐C 5 H 3 (SiMe 2 ‐η 1 ‐N t Bu) 2 }R] and ansa ‐[M{η 5 ‐C 5 H 3 [SiMe 2 (NH t Bu)] (SiMe 2 ‐η 1 ‐N t Bu)}R 2 ] (M = Ti, Zr; R = NMe 2 , CH 2 Ph) complexes with NEt 3 ·HCl have afforded the dichloro derivatives [M{η 5 ‐C 5 H 3 [SiMe 2 (NH t Bu)] (SiMe 2 ‐η 1 ‐N t Bu)}Cl 2 ] [M = Ti ( 6 ), Zr ( 12 )], the amine‐coordinated zirconium compound [Zr{η 5 ‐C 5 H 3 [SiMe 2 (NH t Bu)](SiMe 2 ‐η 1 ‐N t Bu)} Cl 2 (NMe 2 H)] ( 9 ) and the chloro‐benzyl titanium complex [Ti{η 5 ‐C 5 H 3 [SiMe 2 (NH t Bu)](SiMe 2 ‐η 1 ‐N t Bu)}Cl(CH 2 Ph)] ( 11 ). Formation of the mono‐substituted chloroamido zirconium complex [Zr{η 5 ‐C 5 H 3 [SiMe 2 (NH t Bu)](SiMe 2 ‐η 1 ‐N t Bu)}Cl(NMe 2 )] ( 10 ) by the reaction of [Zr{η 5 ‐C 5 H 3 [SiMe 2 (NH t Bu)] (SiMe 2 ‐η 1 ‐N t Bu)}(NMe 2 ) 2 ] with SiClMe 3 has been monitored in C 6 D 6 by NMR spectroscopy. All of the new chloro complexes have been characterized by elemental analyses and NMR spectroscopy and the X‐ray crystal structure of [Ti(η 5 ‐C 5 H 3 {SiMe 2 (NH t Bu)} 2 )Cl 3 ] ( 3 ) has been studied by diffraction methods. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)