New Pyridine Dicarbene Pincer Ligands with Ring Expanded NHCs and their Nickel and Chromium Complexes.

The pincer complexes [Ni II Br(CNC)]Br (4), [Cr III Br 3 (CNC)] (5 a) and [Cr III Br 2.3 Cl 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)Br 2 and [Ni II Br 2 (PPh 3 ) 2 ] or from [Cr II {N(SiMe 3 ) 2 } 2 (THF) 2 ] and (CHNCH)Br 2 by aminolysis, respectively. The tetrahedrally distorted square planar (τ 4 ≅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 CH 2 Cl 2 . 4/MAO and 5 a/MAO were catalysts of moderate activity for the oligomerization and polymerization of ethylene, respectively. The analogous (CH^N^CH)Br 2 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.