biostudies-literatureLim JHDeutsche ForschungsgemeinschaftAgency for Science, Technology and Research (A*STAR)Nanyang Technological UniversityMinistry of Education - Singapore3992-4002https://www.ebi.ac.uk/biostudies/studies/S-EPMC5944818biostudies-literatureUnknown9(16)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]<suChemical scienceC-H activation and nucleophilic substitution in a photochemically generated high valent iron complex.PMC5944818Nanyang Assistant Professorship (M4081154)M4011791A1783c0003M4011611A1783c0002Corby SGanguly RLim JHRay KSoo HSEngelmann XfalseC-H activation and nucleophilic substitution in a photochemically generated high valent iron complex.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]<su2018-01-01T00:00:00Z2018 Apr2026-05-06T03:26:11.733Z2019-03-26T23:40:05ZS-EPMC59448182986200410.1039/c7sc05378a