Computational prediction and analysis of the 27Al solid-state NMR spectrum of methylaluminoxane (MAO) at variable temperatures and field strengths. Issue 34 (15th August 2016)

• Record Type: Journal Article
• Authors: Falls, Zackary; Zurek, Eva; Autschbach, Jochen
• Is Part Of: Physical chemistry chemical physics. Volume 18:Issue 34(2016)
• Page Start: 24106
• Page End: 24118
• Publication Date: 2016-08-15
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c6cp04260k
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : 27 Al MAS NMR of the co-catalyst methylaluminoxane may be able to reveal the fraction of species that are catalytically active. Abstract : Calculations of NMR shielding tensors and nuclear quadrupole coupling (NQC) tensors at the Kohn–Sham density functional level are used to simulate 27 Al magic-angle spinning (MAS) NMR spectra of the important olefin polymerization co-catalyst methylaluminoxane (MAO) at 77, 298, 398, and 498 K and spectrometer magnetic field inductions B ranging from 14.1 to 23.5 T. The calculations utilize the temperature ( T ) dependent distribution of species present in MAO determined recently by Zurek and coworkers from first-principles theory [ Macromolecules, 2014, 47, 8556]. The NMR calculations suggest that variable- T and variable- B NMR measurements are able to quantify the ratio of free versus bound trimethyl-aluminum (TMA) in MAO via characteristic spectral features assigned to 3-coordinate and 4-coordinate Al sites in MAO as well as spectral features arising from free TMA or its dimer. The T -dependent distribution of species causes other characteristic features in the NMR spectra to appear/disappear that can be associated with different aluminum environments such as square vs. hexagonal faces in cage and tubular structures. The simulated spectra at 298 K and 19.6 T are in reasonably good agreement with the experimental solid-state NMR (SSNMR) spectra obtained previously for MAO gel. The promise and limitations of solid-state NMR to unravel the enigma surrounding the structure(s) of MAO are discussed.