Repozytorium
Wyszukaj
Kolekcje
Inne
Reactions of methyl- and ethylaluminium compounds with alkoxyalcohols. The influence of alkoxyalcohol substituents on the structure of the complexes formed.
Autorzy
Rok wydania
2002
Czasopismo
Numer woluminu
334
Strony
385-394
DOI
S0020-1693(02)00859-9
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Dimeric dimethylaluminium compounds {[Me2Al(μ-OCH2CH2OnPr)]2 (1), [Me2Al(μ-OCH(CH3)CH2OtBu)]2 (3), [Me2Al(μ-OCH2CH2CH2OEt)]2 (5), [Me2Al(μ-OCH2CH2CH(Me)OMe)]2 (7), [Me2Al(μ-OCH2CH2C(Me)2OMe)]2 (9)} and dichloroaluminium compounds {[Cl2Al(μ-OCH2CH2OnPr)]2 (2), [Cl2Al(μ-OCH(CH3)CH2OtBu)]2 (4), [Cl2Al(μ-OCH2CH2CH2OEt)]2 (6), [Cl2Al(μ-OCH2CH2CH(Me)OMe)]2 (8), [Cl2Al(μ-OCH2CH2C(Me)2OMe)]2 (10)} have been prepared. The molecular structures of compounds 2, 3, 6, 8, 9 and 10 have been determined by X-ray crystallography. All these compounds exist in the solid state as dimers with chelating ether-alkoxide ligands and five-coordinate aluminium atoms. Dichloroaluminium derivatives (compounds 2, 4, 6, 8 and 10) exist as five-coordinate isomers also in solution, while dimethylaluminium ones (compounds 1, 3, 5, 7 and 9) exist as an equilibrium mixture between four- and five-coordinate isomers. An increase of aluminium Lewis acidity in dichloroaluminium derivatives in comparison with dimethylaluminium ones results in substantial shortening of AlO distances. The R2Al⋯O(ether)R′ distance is mainly determined by the steric repulsion between the OR′ group and the two alkyl substituents on aluminium. The influence of electronic properties of R′ on Cl2Al⋯O(ether)R′ interaction was illustrated for compound 2 in comparison with literature data for analogous complexes. A number of dimethylaluminium and dichloroaluminium compounds containing alkoxyalcoholate ligands have been synthesised by reactions of trimethylaluminium and dichloroalkylaluminium with corresponding alkoxyalcohol. Single crystal X-ray diffraction studies show that all these compounds exist in the solid state as dimers with chelating ether-alkoxide ligands and five-coordinate aluminium atoms. Dichloroaluminium derivatives exist as five-coordinate isomers also in solution, while dimethylaluminium ones exist as an equilibrium mixture between four- and five-coordinate isomers. An increase of aluminium Lewis acidity in dichloroaluminium derivatives in comparison with dimethylaluminium ones results in substantial shortening of AlO distances. The R2Al⋯O(ether)R′ distance is mainly determined by the steric repulsion between the OR′ group and the two alkyl substituents on aluminium.
Słowa kluczowe
Aluminium, Aluminium alkoxide, Alkoxyalcoholate, Crystal structures
Adres publiczny
https://doi.org/10.1016/S0020-1693(02)00859-9
Strona internetowa wydawcy
Podobne publikacje
Synthesis, properties and crystal structures of ionic [Al2(μ,η2-thffo)2(EtOH)4Cl2]Cl2, [Al3(μ,η2-thffo)4Cl4][AlEtCl3] and tetranuclear [Al4(μ,η2-thffo)4(μ-OEt)2Cl6] (thffo = OCH2CH(CH2)3O) compounds.
Sobota Piotr, Utko Józef, Brusilovets A. I., Jerzykiewicz Lucjan B.
The crystal structure and properties of TiCl4{CH(CO2Et)3}] and [Al2Cl6{μ-C2H4(CO2Et)2}].
Sobota Piotr, Szafert Sławomir, Głowiak Tadeusz
Searching for new aluminium chelating agents: a family of hydroxypyrone ligands.
Toso Leonardo, Crisponi Guido, Nurchi Valeria Marina, Crespo-Alonso Miriam, Lachowicz Joanna Izabela, Mansoori Delara, Arca Massimiliano, Santos M. Amélia, Marques Sergio M., Gano Lurdes, Niclós-Gutíerrez Juan, González-Pérez Josefa M., Domínguez-Martín Alicia, Choquesillo-Lazarte Duane, Szewczuk Zbigniew