Isomerization pathway of a C–C sigma bond in a bis(octaazamacrocycle)dinickel(II) complex activated by deprotonation: a DFT study
- Author(s)
- Ingrid Jelemenska, Michal Zalibera, Peter Rapta, Anatolie Dobrov, Vladimir B. Arion, Lukas Bucinsky
- 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.
- Organisation(s)
- Department of Inorganic Chemistry, Department of Biophysical Chemistry
- External organisation(s)
- Slovak University of Technology in Bratislava
- Journal
- Theoretical Chemistry Accounts
- Volume
- 143
- ISSN
- 1432-881X
- DOI
- https://doi.org/10.1007/s00214-024-03100-5
- Publication date
- 04-2024
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 104022 Theoretical chemistry, 104017 Physical chemistry
- Keywords
- ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/df444ea3-18d2-4cfa-97a8-7b93bacadb73