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Cyclopentadienyl–Silsesquioxane Titanium Catalysts: Factors Affecting Their Formation and Activity in Olefin Epoxidation with Aqueous Hydrogen Peroxide
Author(s) -
Ventura María,
Tabernero Vanessa,
Cuenca Tomás,
Royo Beatriz,
Jiménez Gerardo
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501474
Subject(s) - chemistry , cyclopentadienyl complex , silsesquioxane , hydrosilylation , catalysis , titanium , medicinal chemistry , hydrogen peroxide , aqueous solution , solvent , polymer chemistry , organic chemistry , polymer
The reaction of titanium chlorosilyl‐substituted cyclopentadienyl (Cp) complexes, Ti(η 5 ‐C 5 H 3 R′SiMe 2 Cl)Cl 3 (R′ = H, 1b ; SiMe 3 , 1c ), with 1 equiv. of various silsesquioxane trisilanols, R 7 Si 7 O 9 (OH) 3 (R = i Bu, 2a ; Ph, 2b ), affords either corner‐capped Cp derivatives, Ti(η 5 ‐C 5 H 3 R′SiMe 2 Cl)(R 7 Si 7 O 12 ‐κ 3 O 3 ) (R′ = H, R = i Bu, 5a , Ph, 5b ; R′ = SiMe 3 , R = i Bu, 7a , Ph, 7b ), or cyclopentadienyl–silsesquioxane complexes, Ti(η 5 ‐C 5 H 4 SiMe 2 OR 7 Si 7 O 11 ‐κ 2 O 2 )Cl (R′ = H, R = i Bu, 6a , Ph, 6b ; R′ = SiMe 3 , R = i Bu, 8a , Ph, 8b ), depending on the reaction conditions. In any case, upon heating, kinetic products 5 and 7 are transformed into the corresponding thermodynamic products 6 and 8 , respectively. The electron‐donating ability of the Cp ring is a relevant controlling parameter: a strong π‐donor character facilitates the isomerization process. In addition, the nature of the silicon substituents in the silsesquioxane framework, the type of solvent, and the reaction temperature are also factors that significantly affect this process. Cyclopentadienyl–silsesquioxane complexes 6b and 8b are efficient and selective catalysts for epoxidation with aqueous hydrogen peroxide under mild conditions. Such a catalytic efficiency is attributed to the hydrophobic environment generated about the titanium atom by the Cp ring incorporated into the cyclopentadienyl–silsesquioxane ligand.