0000000000222214
AUTHOR
Michal Horáček
Preparation of titanocene and zirconocene dichlorides bearing bulky 1,4-dimethyl-2,3-diphenylcyclopentadienyl ligand and their behavior in polymerization of ethylene
Abstract New metallocene dichlorides [η 5 -(1,4-Me 2 -2,3-Ph 2 -C 5 H) 2 TiCl 2 ] ( 2 ), [η 5 -(1,4-Me 2 -2,3-Ph 2 -C 5 H) 2 ZrCl 2 ] ( 3 ) and [η 5 -(1,4-Me 2 -2,3-Ph 2 -C 5 H)η 5 -(C 5 H 5 )ZrCl 2 ] ( 4 ) were prepared from lithium salt of 1,4-dimethyl-2,3-diphenylcyclopentadiene ( 1 ) and [TiCl 3 (THF) 3 ], [ZrCl 4 ] and [η 5 -(C 5 H 5 )ZrCl 3 (DME)], respectively. Compounds 2–4 were characterized by NMR spectroscopy, EI-MS and IR spectroscopy, and the solid state structure of 3 was determined by single crystal X-ray crystallography. The catalytic systems 3 /MAO and 4 /MAO were almost inactive in polymerization of ethylene at 30–50 °C, however, they exhibited high activity at temperature…
Reactions of titanocene-bis(trimethylsilyl)ethyne complexes with diethynylsilane derivatives
Titanocene complexes [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 4 and 5) react uniformly with siladiynes R 2 2 Si(CCR 1 ) 2 , where R 1 =Ph, and R 2 =Ph or Me, at elevated temperature in hydrocarbon solvents to give the corresponding silacyclobutene-annelated titanacyclobutene complexes, 3-bis(η 5 -cyclopentadienyl)titana-6-diorganylsilabicyclo[2.2.0]hexa-1(2),4(5)-dienes, [(η 5 -C 5 H 5− n Me n ) 2 Ti{R 1 2 C 4 (SiR 2 2 )}]. Products arising from [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 2 (1,3-isomer), 4 and 5) and Me 2 Si(CCCMe 3 ) 2 vary with n : the non-methylated titanocene complex affords a mixture of an analogous silacyclobutene-annelated t…
Syntheses and properties of some exo,exo-bis(isodicyclopentadienyl)titanium low-valent complexes
Abstract The paramagnetic compounds exo,exo-bis(η5-isodicyclopentadienyl)chlorotitanium(III) (3) and its analogue with trimethylsilyl-substituted isodicyclopentadienide (isodiCp) ligand (4), and the similar pair of diamagnetic exo,exo-bis(isodicyclopentadienyl)[η2-bis(trimethylsilyl)ethyne]titanium(II) complexes 5 and 6 were obtained by common reduction procedures from exo,exo-bis(isodicyclopentadienyl)titanium(IV) dichloride (1) and exo,exo-bis[η5-2-(trimethylsilyl)isodicyclopentadienyl]titanium(IV) dichloride (2), respectively. As indicated by ESR spectroscopy compound 3 is a dimer in the solid state and in frozen toluene glass but monomeric in toluene solution. Compound 4 is monomeric in…
Titanium and zirconium complexes containing the new 2,3-dimethyl-1,4-diphenylcyclopentadienyl ligand. Synthesis, characterization and polymerization behavior
Abstract An easy and inexpensive three-step synthesis of new 2,3-dimethyl-1,4-diphenylcyclopentadiene (3) ligand and the titanium and zirconium homometallocene dichlorides [TiCl2(η5-C5H-2,3-Me2-1,4-Ph2)2] (4), [ZrCl2(η5-C5H-2,3-Me2-1,4-Ph2)2] (5), and the mixed ligand zirconium complex [ZrCl2(η5-C5H-2,3-Me2-1,4-Ph2)(η5-C5H5)] (6) prepared thereof are described. The polymerization of ethene using 4–6/MAO catalysts revealed that zirconocene complexes 5 and 6 displayed moderate and high activity, respectively, whereas the titanium catalyst 4/MAO was inactive. The crystal structures of 4 and 5 were determined by X-ray crystallography.