Dichloro(methyl)silyl-substituted cyclopentadienyl titanium complexes

Abstract

Ž.Ž .Ž .

Aryl-imido niobium complexes with chloro-silyl and aryl-η-amidosilyl cyclopentadienyl ligands: X-ray structure of the constrained-geometry compound [Nb(η5-C5H4SiMe2-η1-NAr)(NAr)Cl] (Ar=2,6-Me2C6H3)

“…The selective hydrolysis of the Si-Cl bond with formation of a Si-O-Si bridge was the expected behaviour for this type of niobium compound [11,27]. In contrast, it was observed [6,[30][31][32][33] that the hydrolysis reactions of related monocyclopentadienyl group 4 metal complexes with Scheme 1. the chloro-silylcyclopentadienyl ligand afforded Si-O-M bridges. Attempts to produce further hydrolysis of NbCl bonds failed and led to decomposition products with elimination of the corresponding amine.…”

Synthesis and reactivity of imido niobium complexes containing the functionalized (dichloromethylsilyl)cyclopentadienyl ligand

“…LiNHtBu was prepared in hexane in quantitative yield from tBuNH 2 and nBuLi (Aldrich, 1.6 M in hexane). C 5 H 4 (SiCl 2 Me)(SiMe 3 ) [28] was prepared according to the literature procedures. (2) A solution of lithium amide LiNHtBu (1.21 g, 15.38 mmol) in toluene (40 mL) was added dropwise to a previously cooled (À78°C) solution of 1 (3.17 g, 7.69 mmol) and NEt 3 (1.07 mL, 7.69 mmol) in toluene (50 mL).…”

“…These two types of compounds offered the opportunity to introduce a chelating cyclopentadienyl silyl-g-amido ligand whilst still leaving a second reactive point at the cyclopentadienyl ligand. The first type of complex can be illustrated by the reported constrained geometry group 4 metal complexes with one additional Si-X bond (X = H, Cl, NHtBu) [28][29][30], which were suitable to explore further reactivity of these bonds. Furthermore, hydrolysis of the Si-Cl bond of the starting [Ti{g 5 -C 5 R 4 (SiCl 2 Me)}Cl 3 ] (R = H, Me) complexes gave dinuclear compounds with Si-O-Ti [28] bridges and one additional Si-O-Si bridge (for R = Me) [31].…”

“…The first type of complex can be illustrated by the reported constrained geometry group 4 metal complexes with one additional Si-X bond (X = H, Cl, NHtBu) [28][29][30], which were suitable to explore further reactivity of these bonds. Furthermore, hydrolysis of the Si-Cl bond of the starting [Ti{g 5 -C 5 R 4 (SiCl 2 Me)}Cl 3 ] (R = H, Me) complexes gave dinuclear compounds with Si-O-Ti [28] bridges and one additional Si-O-Si bridge (for R = Me) [31]. The second type of compound comprised the bis(silyl-gamido)cyclopentadienyl group 4 metal complexes, which were synthesized [14] and studied as a new type of olefin polymerization catalysts.…”

Synthesis and characterization of η5-tetramethylcyclopentadienyl-hydrido- and -chloro-silyl-η1-amido zirconium complexes

“…for C 18 H 37 N 3 SiZr: C,52.12;H,8.99;N,10.13. Found: C,51.24;H,8.88;N,9 10.9, 11.1, 12.7, 13.5 (C 5 (10) A 1.02 M solution of MgCl(C 6 F 5 ) in diethyl ether (4.0 ml, 4.0 mmol) was added to a solution of 6 (0.8 g, 2 mmol) in diethyl ether (50 ml) cooled at (/78 8C. The reaction mixture was slowly warmed to r.t. and then stirred for 16 h. The volatiles were removed under reduced pressure and the residue was extracted into hexane (60 ml).…”