Exploiting Noncovalent Interactions for Room-Temperature Heteroselective rac-Lactide Polymerization Using Aluminum Catalysts

A1 Originalartikel i en vetenskaplig tidskrift (referentgranskad)


Interna författare/redaktörer


Publikationens författare: S. Gesslbauer, R. Savela, Y. Chen, A. J. P. White, C. Romain
Förläggare: American Chemical Society
Publiceringsår: 2019
Tidskrift: ACS Catalysis
Tidskriftsakronym: ACS Catal.
Volym: 9
Artikelns första sida, sidnummer: 7912
Artikelns sista sida, sidnummer: 7920


Abstrakt

Whereas harnessing noncovalent interactions (NCIs) has largely been
applied to late-transition-metal complexes and to the corresponding
catalytic reactions, there are very few examples showing the importance
of NCIs in early-transition-metal and main-group-metal catalysis. Here,
we report on the effects of hydrogen bond donors in the catalytic pocket
to explain the high activity and stereoselectivity of a series of
aluminum catam complexes in rac-lactide ring-opening polymerization (ROP). Four original aluminum catam
catalysts have been synthesized and fully characterized.
Structure–activity relationships and isotope effects show the importance
of the NH moieties of the ligand in rac-lactide ROP.
Computational studies highlight beneficial hydrogen bonds between the
ligand and the monomer. Overall, structural characterization of the
catalysts and mechanistic, kinetic, and computational studies support
the benefits of noncovalent interactions in the catalytic pocket.


Senast uppdaterad 2020-18-02 vid 02:58