Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 46, Pages 14384-14388Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201707872
Keywords
hydrogen atom transfer; O ligands; oxoiron(IV) complexes; oxygen atom transfer; spin state
Categories
Funding
- DFG (Cluster of Excellence Unifying Concepts in Catalysis) [EXC 314-2]
- MINECO [CTQ2014-59212-P, CTQ2015-70851-ERC]
- GenCat [2014SGR1202]
- FEDER [UNGI10-4E-801]
- COST action [CM1305]
- DFG
- NTU
- NRF of Korea through CRI [NRF-2012R1A3A2048842]
- GRL [NRF-2010-00353]
- Basic Science Research Program [2017R1D1A1B03029982]
- DOE Office of Science [DE-AC02-76SF00515]
- NIH [P30-EB-009998, P41-GM-103393]
- National Research Foundation of Korea [2017R1D1A1B03029982, 2012R1A3A2048842] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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The sluggish oxidants [Fe-IV(O)(TMC)(CH3CN)](2+) (TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and [Fe-IV(O)(TMCN-d(12))(OTf)](+) (TMCN-d(12)= 1,4,7,11-tetra(methyl-d(3))-1,4,7,11-tetraazacyclotetradecane) are transformed into the highly reactive oxidant [Fe-IV(O)-(TMCO)(OTf)](+) (1; TMCO=4,8,12-trimethyl-1-oxa-4,8,12-triazacyclotetradecane) upon replacement of an NMe donor in the TMC and TMCN ligands by an O atom. A rate enhancement of five to six orders of magnitude in both H atom and O atom transfer reactions was observed upon oxygen incorporation into the macrocyclic ligand. This finding was explained in terms of the higher electrophilicity of the iron center and the higher availability of the more reactive S=2 state in 1. This rationalizes nature's preference for using O-rich ligand environments for the hydroxylation of strong C-H bonds in enzymatic reactions.
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