Summary :

Pyridine Ring-Expanded dicarbene Pincer ligands were synthesized and some representative complexes with Ni and Cr show distinct geometrical and electronic characteristics from analogues with 5-membered ring heterocycles, opening new possibilities for pincer ligands featuring carbene donors.

Abstract:

The pincer complexes [Ni^IIBr(CNC)]Br (4), [Cr^IIIBr₃(CNC)] (5 a) and [Cr^IIIBr_2.3Cl_0.7(CNC)] (5 b), where CNC=3,3′-(pyridine-2,6-diyl)bis(1-mesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene), were obtained from the novel ligand CNC, generated in situ from the precursor (CHNCH)Br₂ and [Ni^IIBr₂(PPh₃)₂] or from [Cr^II{N(SiMe₃)₂}₂(THF)₂] and (CHNCH)Br₂ by aminolysis, respectively. The tetrahedrally distorted square planar (τ₄≅0.30) geometry and the singlet ground state of Ni in 4 were attributed to steric constraints of the CNC backbone. Computational methods highlighted the dependence of the coordination geometry and the singlet-triplet energy difference on the size of the N-substituent of the tetrahydropyrimidine wingtips and contrasted it to the situation in 5-membered imidazolin-2-ylidene pincer analogues. The octahedral Cr^III metal center in 5 a and 5 b is presumably formed after one electron oxidation from CH₂Cl₂. 4/MAO and 5 a/MAO were catalysts of moderate activity for the oligomerization and polymerization of ethylene, respectively. The analogous (CH^N^CH)Br₂ precursor, where (CH^N^CH)=3,3′-(pyridine-2,6-diylbis(methylene))bis(1-mesityl-3,4,5,6-tetrahydropyrimidin-1-ium), was also prepared, however its coordination chemistry was not studied due to the inherent instability of the resulting free C^N^C ligand.

Graphical Abstract:

 

Reference:

Pyridine Dicarbene Ligand Designs with Ring Expanded NHCs: Steric and Electronic Tuning of and Catalysis with Nickel and Chromium Complexes

Evangelos Papangelis,Katrin Pelzer,Christophe Gourlaouen, Dominique Armspach,Pierre Braunstein,Andreas A. Danopoulos, Corinne Baillyand Nikolaos Tsoureas

Chem Asian J. 2024 – DOI: https://doi.org/10.1002/asia.202400169

Contact:

Pierre Braunstein (équipe ECMC, ancien Directeur de l’équipe  LCC), Institut de Chimie (UMR 7177).