Back to Search
Start Over
DFT analysis of the electronic structure of Fe(IV) species active in nitrene transfer catalysis: influence of the coordination sphere
- Source :
- Journal of Molecular Modeling, Journal of Molecular Modeling, Springer Verlag (Germany), 2016, 22 (11), pp.article number 278. ⟨10.1007/s00894-016-3142-6⟩, Journal of Molecular Modeling, 2016, 22 (11), pp.article number 278. ⟨10.1007/s00894-016-3142-6⟩
- Publication Year :
- 2016
- Publisher :
- Springer Science and Business Media LLC, 2016.
-
Abstract
- International audience; Nitrene transfer reactions to various hydrocarbon molecules can be efficiently catalyzed by Fe complexes through a mechanism reminiscent of the oxygen transfer function of oxygenase enzymes. Such enzymes exhibit a high-valent iron oxo Fe(IV) = O as the active species, and it has also been proposed that an analogous species, i.e., Fe(IV) = NR (NR being the nitrene group) is responsible for the nitrene transfer activity. We describe here the influence of the Fe(IV) coordination sphere on some key parameters for nitrene transfer efficacy, such as the spin state of the Fe(IV) cation, the electronic affinity, and the bond dissociation energy of the NHR moiety. We explore here the electronic properties of Fe(IV) = NTs (NTs = tolylsulfonylimido group) mononuclear complexes with ligands involving phenolate and nitrogen donor groups, as catalytic properties with such ligands have been found to be quite promising. Six tetradentate ligands were studied, which derive from three different scaffolds: 2-methylenepyridine-N,N-bis(2-methylene-4,6-dichlorophenol) and 2-methylenepyridine-N,N-bis(2-methylene-4,6-dimethylphenol), N,N-dimethyl-N’,N’-bis(2-methylene-4,6-dichlorophenol) ethylenediamine, and N,N-dimethyl-N’,N’- bis(2-methylene-4,6-dimethylphenol) ethylenediamine, N,N’-bis(2-methylene-4,6-dichlorophenol)-N,N’-dimethyl-1,2-diaminoethane and N,N’-bis(2-methylene-4,6-dimethylphenol)-N,N’-dimethyl-1,2-diaminoethane. Thanks to thorough DFT computations, we present some rationalization of the electronic properties of the resulting Fe(IV) = NTs complexes in relation to their coordination sphere and compare them to other Fe(IV) nitrene active species. We show in particular the important role of the anionic character and strong π-donation of the phenolate groups.
- Subjects :
- Coordination sphere
Spin states
Nitrene
Nitrene transfer
Ethylenediamine
010402 general chemistry
Photochemistry
DFT
01 natural sciences
Catalysis
Inorganic Chemistry
chemistry.chemical_compound
Moiety
Molecule
[CHIM.COOR]Chemical Sciences/Coordination chemistry
Physical and Theoretical Chemistry
010405 organic chemistry
Chemistry
Organic Chemistry
[CHIM.CATA]Chemical Sciences/Catalysis
[INFO.INFO-MO]Computer Science [cs]/Modeling and Simulation
Bond-dissociation energy
0104 chemical sciences
Computer Science Applications
Electronic affinity
Crystallography
Computational Theory and Mathematics
Fe(IV) imido
Bond dissociation energy
Subjects
Details
- ISSN :
- 09485023 and 16102940
- Volume :
- 22
- Database :
- OpenAIRE
- Journal :
- Journal of Molecular Modeling
- Accession number :
- edsair.doi.dedup.....6982eff19754c266881a66215e43d06c