Back to Search
Start Over
Unmasking Steps in Intramolecular Aromatic Hydroxylation by a Synthetic Nonheme Oxoiron(IV) Complex.
- Source :
-
Angewandte Chemie . 9/13/2021, Vol. 133 Issue 38, p21159-21166. 8p. - Publication Year :
- 2021
-
Abstract
- In this study, a methyl group on the classic tetramethylcyclam (TMC) ligand framework is replaced with a benzylic group to form the metastable [FeIV(Osyn)(Bn3MC)]2+ (2‐syn; Bn3MC=1‐benzyl‐4,8,11‐trimethyl‐1,4,8,11‐tetraazacyclotetradecane) species at −40 °C. The decay of 2‐syn with time at 25 °C allows the unprecedented monitoring of the steps involved in the intramolecular hydroxylation of the ligand phenyl ring to form the major FeIII−OAr product 3. At the same time, the FeII(Bn3MC)2+ (1) precursor to 2‐syn is re‐generated in a 1:2 molar ratio relative to 3, accounting for the first time for all the electrons involved and all the Fe species derived from 2‐syn as shown in the following balanced equation: 3 [FeIV(O)(LPh)]2+ (2‐syn)→2 [FeIII(LOAr)]2+ (3)+[FeII(LPh)]2+ (1)+H2O. This system thus serves as a paradigm for aryl hydroxylation by FeIV=O oxidants described thus far. It is also observed that 2‐syn can be intercepted by certain hydrocarbon substrates, thereby providing a means to assess the relative energetics of aliphatic and aromatic C−H hydroxylation in this system. [ABSTRACT FROM AUTHOR]
- Subjects :
- *HYDROXYLATION
*BENZYLIC group
*METHYL groups
*OXIDIZING agents
Subjects
Details
- Language :
- English
- ISSN :
- 00448249
- Volume :
- 133
- Issue :
- 38
- Database :
- Academic Search Index
- Journal :
- Angewandte Chemie
- Publication Type :
- Academic Journal
- Accession number :
- 152292127
- Full Text :
- https://doi.org/10.1002/ange.202108309