The metallocene/methylaluminoxane catalysts formation: EPR spin probe study of Lewis acidic sites of methylaluminoxane

Citation
Ep. Talsi et al., The metallocene/methylaluminoxane catalysts formation: EPR spin probe study of Lewis acidic sites of methylaluminoxane, J MOL CAT A, 139(2-3), 1999, pp. 131-137
Citations number
18
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
ISSN journal
13811169 → ACNP
Volume
139
Issue
2-3
Year of publication
1999
Pages
131 - 137
Database
ISI
SICI code
1381-1169(19990305)139:2-3<131:TMCFES>2.0.ZU;2-V
Abstract
Using stable nitroxyl radical 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) as a spin probe, Lewis acidic sites of methylaluminoxane (MAO) were identif ied. It was found that MAO contains two types of acidic sites. TEMPO, coord inated to the sires I and II, exhibits in the EPR spectra triplet (g(o) = 2 .0047, a(N) = 18.6 G) and triplet of sextets (g(o) = 2.0045, a(N) = 19.6 G and a(Al) = 1.7 G), respectively (a(N) and a(Al) are constants of hyperfine structure from the corresponding nucleus). According to EPR measurements, concentration of sites I is close to that of sites II, and MAO contains one site of each type per 100 +/- 30 aluminium atoms. The adducts of TEMPO wit h sites I are less stable than those with sites II. Based on the values of a(Al) and relative stabilities of the adducts with TEMPO, the acidic sites I and II were attributed to coordinatively unsaturated aluminium atoms in A lOMe2 and AlO2Me environment, respectively. From the EPR spectra of coordin ated TEMPO, the average radius of MAO oligomers (AlOMe)(n) was evaluated to be 5.8 Angstrom at 20 degrees C, which corresponds to the value of n = 15- 20. Thus, the major part of MAO contains not more than one Lewis acidic sit e per one oligomeric (AlOMe)(n) molecule. (C) 1999 Elsevier Science B.V. Al l rights reserved.