Phenoxyimines (FI) and Salen are ubiquitous ligands that are widely used, particularly in organometallic catalysis, with various industrial applications. However, one inherent drawback of their structure is the presence of electrophilic imine(s), which can react and cause a deleterious drop in catalytic performance. MORFAL aims at developing a related class of FI and Salen ligands, where the imine function will be replaced by a trisubstituted amidine giving rise to new phenoxy-amidine ligands (FA). The amidine moiety should provide higher stability and electron-donating ability making FA ligands particularly well suited for stabilising highly reactive cationic or neutral metal species. Considering that the hard character of FA ligands (N,O donor atoms) is best suited for early metals, the coordinating ability of FA ligands will be studied with group 2-4 elements. FA group 4 metal complexes will be targeted for the production of UHMWPE and for the stereoselective polymerisation of propylene. The use of FA ligands more tolerant to alkylating or reducing agent than FI should facilitate the access to well define active cationic species for olefin polymerisation and prevent alkylation and/or reduction of the ligand backbone during the polymerisation reaction. The sigma and ?-donor ability of FA ligands should also contribute to enhance the thermal stability of the active cationic species and thus allow to maintain high catalytic performance when more drastic reaction conditions (temperature, pressure) are required. MORFAL aims also at developing FA-based catalysts for hydrophosphination reaction from early transition metals or even the large alkaline earths Ca-Ba. Special attention will be paid to promote asymmetric catalytic HP using chiral FA early metal complexes. FA ligands are expected to be more suitable than FI for this reaction, which otherwise can undergo intramolecular hydrophosphination.
Monsieur Pierre Le Gendre (INSTITUT DE CHIMIE MOLECULAIRE DE L'UNIVERSITE DE BOURGOGNE - UMR 6302)
The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.
ICMUB INSTITUT DE CHIMIE MOLECULAIRE DE L'UNIVERSITE DE BOURGOGNE - UMR 6302
ISCR Université Rennes 1
Help of the ANR 380,014 euros
Beginning and duration of the scientific project: March 2023 - 42 Months