C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex† †Electronic supplementary information (ESI) available: Detailed synthetic procedures and characterisation. CCDC 1535587. For ESI and crystallographic data in CIF or other electronic format see DOI:

Content Provider	Semantic Scholar
Author	Lim, Jia Hui Hazel Engelmann, Xenia Corby, Sacha Ganguly, Rakesh Ray, Kallol Soo, Han Sen
Copyright Year	2018
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.
Starting Page	3992
Ending Page	4002
Page Count	11
File Format	PDF HTM / HTML
Alternate Webpage(s)	http://pubs.rsc.org/en/content/articlepdf/2018/sc/c7sc05378a?page=search
Alternate Webpage(s)	https://dr.ntu.edu.sg/bitstream/handle/10220/45358/C%E2%80%93H%20activation%20and%20nucleophilic%20substitution%20in%20a%20photochemically%20generated%20high%20valent%20iron%20complex.pdf?isAllowed=y&sequence=1
PubMed reference number	5944818
Alternate Webpage(s)	https://doi.org/10.1039/c7sc05378a
DOI	10.1039/c7sc05378a
Journal	Chemical science
Volume Number	9
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article