Please use this identifier to cite or link to this item:
https://hdl.handle.net/10356/87434
Title: | C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex | Authors: | Lim, Jia Hui Engelmann, Xenia Corby, Sacha Ganguly, Rakesh Ray, Kallol Soo, Han Sen |
Keywords: | C–H Activation Nucleophilic |
Issue Date: | 2018 | Source: | Lim, J. H., Engelmann, X., Corby, S., Ganguly, R., Ray, K., & Soo, H. S. (2018). C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex. Chemical Science, 9(16), 3992-4002. | Series/Report no.: | Chemical Science | Abstract: | The photochemical oxidation of a (TAML)FeIII complex 1 using visible light generated Ru(bpy)33+ produces valence tautomers (TAML)FeIV (1+) and (TAML˙+)FeIII (1-TAML˙+), depending on the exogenous anions. The presence of labile Cl− or Br− results in a ligand-based oxidation and stabilisation of a radical-cationic (TAML˙+)FeIII complex, which subsequently leads to unprecedented C–H activation followed by nucleophilic substitution on the TAML aryl ring. In contrast, exogenous cyanide culminates in metal-based oxidation, yielding the first example of a crystallographically characterised S = 1 [(TAML)FeIV(CN)2]2− species. This is a rare report of an anion-dependent valence tautomerisation in photochemically accessed high valent (TAML)Fe systems with potential applications in the oxidation of pollutants, hydrocarbons, and water. Furthermore, the nucleophilic aromatic halogenation reaction mediated by (TAML˙+)FeIII represents a novel domain for high-valent metal reactivity and highlights the possible intramolecular ligand or substrate modification pathways under highly oxidising conditions. Our findings therefore shine light on high-valent metal oxidants based on TAMLs and other potential non-innocent ligands and open new avenues for oxidation catalyst design. | URI: | https://hdl.handle.net/10356/87434 http://hdl.handle.net/10220/45358 |
ISSN: | 2041-6520 | DOI: | 10.1039/C7SC05378A | Schools: | Interdisciplinary Graduate School (IGS) School of Physical and Mathematical Sciences |
Research Centres: | Solar Fuels Laboratory Energy Research Institute @ NTU (ERI@N) |
Rights: | © 2018 The Author(s) (published by Royal Society of Chemistry) . Open Access Article. Published on 23 March 2018. Downloaded on 7/27/2018 6:22:43 AM. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. | Fulltext Permission: | open | Fulltext Availability: | With Fulltext |
Appears in Collections: | SPMS Journal Articles |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex.pdf | 1.48 MB | Adobe PDF | ![]() View/Open |
SCOPUSTM
Citations
20
12
Updated on Sep 17, 2023
Web of ScienceTM
Citations
20
11
Updated on Sep 16, 2023
Page view(s) 50
559
Updated on Sep 23, 2023
Download(s) 50
110
Updated on Sep 23, 2023
Google ScholarTM
Check
Altmetric
Items in DR-NTU are protected by copyright, with all rights reserved, unless otherwise indicated.