Structural characterization of Al10O6iBu16(mu-H)2, a high aluminum content cluster: further studies of methylaluminoxane (MAO) and related aluminum complexes.

The first structurally characterized isobutyl-containing aluminoxane compound is presented. The Al10O6iBu16(mu-H)2 (I) cluster is produced from neat octakis-isobutyltetraluminoxane (Al4O2iBu8) at 80 degrees C in 6-8 h followed by slow crystallization. The crystal is triclinic (space group P1) with the molecule lying on an inversion center.

Activation of metallocenes for olefin polymerization as monitored by IR spectroscopy.

Binary mixtures of Cp2ZrMe2, Cp2ZrCl2, dimethylaluminum chloride, trimethylaluminum, and methylaluminoxane (MAO), as well as Cp2ZrMe2 with boron-based activators, have been studied by in situ IR spectroscopy (Cp = cyclopentadienyl, Me = methyl). The position of a strong band near 800 cm(-1), corresponding to the out-of-plane vibration of the Cp hydrogen atoms, is sensitive to the bonding environment around Zr and can be used to monitor reactions and the formation of new products in these mixtures. Harmonic frequencies determined by density functional theory correlate well with experimental values and have been used to assist in the interpretation of the data.

Tools and strategies for processing diffusion-ordered 2D NMR spectroscopy (DOSY) of a broad, featureless resonance: an application to methylaluminoxane (MAO).

Unlabelled: DOSY has been extremely successful in many studies of molecular weight distributions, especially when the components are separable along the chemical shift axis. However, an unresolved NMR resonance yields the familiar problem of overlapping exponential decays. In a study of methylaluminoxane (MAO), a set of data processing and simulation tools were developed: read Bruker data files (Matlab); preliminary non-linear least-squares fit with f-test (Matlab); movie generation of the fits (Matlab); conversion of diffusion coefficients to molecular masses through molecular volumes (Gaussian-98); and simulation of DOSY data sets for various molecular mass distributions (Mathematica).