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

The pincer complexes [NiIIBr(CNC)]Br (4), [CrIIIBr3(CNC)] (5a) and [CrIIIBr2.3Cl0.7(CNC)] (5b), 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 [NiIIBr2(PPh3)2]...

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Veröffentlicht in:Chemistry, an Asian journal an Asian journal, 2024
Hauptverfasser: Papangelis, Evangelos, Pelzer, Katrin, Gourlaouen, Christophe, Armspach, Dominique, Braunstein, Pierre, Danopoulos, Andreas A., Bailly, Corinne, Tsoureas, Nikolaos, Gerokonstantis, Dimitrios Triantafyllos
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container_title Chemistry, an Asian journal
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creator Papangelis, Evangelos
Pelzer, Katrin
Gourlaouen, Christophe
Armspach, Dominique
Braunstein, Pierre
Danopoulos, Andreas A.
Bailly, Corinne
Tsoureas, Nikolaos
Gerokonstantis, Dimitrios Triantafyllos
description The pincer complexes [NiIIBr(CNC)]Br (4), [CrIIIBr3(CNC)] (5a) and [CrIIIBr2.3Cl0.7(CNC)] (5b), 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 [NiIIBr2(PPh3)2] or from [CrII{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 CrIII metal center in 5a and 5b is presumably formed after one electron oxidation from CH2Cl2. 4/MAO and 5a/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.
doi_str_mv 10.1002/asia.202400169
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title New Pyridine Dicarbene Ligands with Ring Expanded NHCs and their Nickel and Chromium Complexes
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