Isomerization pathway of a C-C sigma bond in a bis(octaazamacrocycle)dinickel(II) complex activated by deprotonation: a DFT study.
Theor Chem Acc
; 143(4): 26, 2024.
Article
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| MEDLINE
| ID: mdl-38495857
ABSTRACT
The anti (a) to syn (s) isomerization pathway of the deprotonated form of the dimer with two nickel(II) 15-membered octaazamacrocyclic units connected via a carbon-carbon (C-C) σ bond was investigated. For the initial anti (a) structure, a deprotonation of one of the bridging (sp3 hybridized) carbon atoms is suggested to allow for an a to s geometry twist. A 360° scan around the bridging C-C dihedral angle was performed first to find an intermediate geometry. Subsequently, the isomerization pathway was explored via individual steps using a series of mode redundant geometry optimizations (internal coordinates potential energy surface scans) and geometry relaxations leading to the s structure. The prominent geometries (intermediates) of the isomerization pathway are chosen and compared to the a and s structures, and geometry relaxations of the protonated forms of selected intermediates are considered. Supplementary Information The online version contains supplementary material available at 10.1007/s00214-024-03100-5.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Theor Chem Acc
Año:
2024
Tipo del documento:
Article
Pais de publicación:
Alemania