jacs%2E6b10609.pdf (2.96 MB)
Dynamic, reversible oxidative addition of highly polar bonds to a transition metal
journal contribution
posted on 2023-06-21, 06:02 authored by Rüdiger Bertermann, Julian Böhnke, Holger Braunschweig, Rian D Dewhurst, Thomas Kupfer, Jonas H Muessig, Leanne Pentecost, Krzysztof Radacki, Sakya S Sen, Alfredo VargasAlfredo VargasThe combination of Pt0 complexes and indium trihalides leads to compounds that form equilibria in solution between their In-X oxidative addition (OA) products (PtII indyl complexes) and their metal-only Lewis pair (MOLP) isomers (LnPt?InX3). The position of the equilibria can be altered reversibly by changing the solvent, while the equilibria can be reversibly and irreversibly driven towards the MOLP products by addition of further donor ligands. The results mark the first observation of an equilibrium between MOLP and OA isomers, as well as the most polar bond ever observed to undergo reversible oxidative addition to a metal complex. In addition, we present the first structural characterization of MOLP and oxidative addition isomers of the same compound. The relative energies of the MOLP and OA isomers were calculated by DFT methods, and the possibility of solvent-mediated isomerization is discussed.
History
Publication status
- Published
File Version
- Accepted version
Journal
Journal of the American Chemical SocietyISSN
1520-5126Publisher
American Chemical SocietyExternal DOI
Issue
49Volume
138Page range
16140-16147Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2016-11-24First Open Access (FOA) Date
2017-11-22First Compliant Deposit (FCD) Date
2016-11-24Usage metrics
Categories
No categories selectedKeywords
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC