Abstract
While aluminum alkyls are often considered to be exemplary compounds of main-group organometallics and an in-depth understanding of their multifaceted chemistry is continually vital, the controlled oxygenation of organoaluminum complexes still remains a largely undeveloped area. In the course of our systematic studies on the relationship between the Lewis acidity of metal centers and noncovalent interactions in the secondary coordination sphere, we report the oxygenation of dialkylaluminum complexes incorporating a pyrrole–ester ligand, as purposefully selected dormant Lewis acidic octet-compliant model compounds, and the isolation and characterization of a new, dimeric aluminum tert-butylperoxide and an unique example of an aluminum oxoethoxide cluster. Our studies provide a more in-depth look at the diversity and complexity of the oxygenation chemistry of aluminum alkyls.
Highlights
While the formation of NRMOOR species was already postulated at the end of 19th century, compounds of this type have been elusive for over 100 years.[2]
Our investigations strongly indicate that formation of the metal alkoxides may be rationalized in terms of an intramolecular rearrangement of nonredox metal alkylperoxides (Scheme 1, path 2).[11,27,28]
Given the pronounced susceptibility of a tert-butyl ligand to stabilize metal alkylperoxide species, we initially investigated oxygenation of the di-tert-butylaluminum chelate complex 1
Summary
Corresponding Author Janusz Lewiński − Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland; Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland; orcid.org/0000-0002-3407-0395; Email: lewin@ ch.pw.edu.pl. Authors Anna Rola-Noworyta − Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland Tomasz Pietrzak − Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland Vadim Szejko − Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland Iwona Justyniak − Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland.
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