Towards a Predictive Conceptual Model for Polymerization of Cyclic Esters Catalyzed by Group 14 Metal Complexes

Project Details

Description

The search for sustainable alternatives for petroleum-based plastics
is one of the key challenges of the modern society. Such
biodegradable bioplastics are synthesized via controllable ringopening polymerization (ROP) of cyclic esters. ROP catalyst
development has recently been dominated by cationic main group
metal complexes. Surprisingly, tin based cationic complexes have
been overlooked so far, despite the fact that the industrial ROP is still
catalyzed by a tin octanoate. The main research goal of this project is
to build a conceptual predictive model for metal and ligand effects in
ROP of selected cyclic esters catalyzed by cationic group 14 metal
complexes. At first, a set of novel N,N-chelating ligands allowing for
the formation of discrete cationic complexes of germanium and tin
will be evaluated. The electronic and steric properties of the resulting
complexes will be then assessed using a combination of conceptual
DFT, energy decomposition analysis and topographic steric maps.
Once a clear picture of the catalysts’ properties is obtained, detailed
mechanistic studies coupled with the activation strain model and the
non-covalent interaction index will be used to reveal the ratedetermining transition states and intermediates. As such, the role of
the ligand, metal and substrate in ROP will be fully rationalized with
this novel conceptual framework, which will ultimately allow for the
determination of a simple mathematical model for the future catalyst
design
AcronymFWOTM1003
StatusActive
Effective start/end date1/10/20 → 30/09/23

Flemish discipline codes

  • Coordination chemistry
  • Main group chemistry
  • Catalysis
  • Quantum chemistry
  • Theoretical and computational chemistry not elsewhere classified

Keywords

  • Density Functional Theory
  • Main Group Metal Catalysis
  • Ring-Opening Polymerization of Cyclic Esters