TY - JOUR
T1 - Facile Conversion of syn-[Fe IV (O)(TMC)] 2+ into the anti Isomer via Meunier's Oxo–Hydroxo Tautomerism Mechanism
AU - Prakash, Jai
AU - Sheng, Yuan
AU - Draksharapu, Apparao
AU - Klein, Johannes E.M.N.
AU - Cramer, Christopher J.
AU - Que, Lawrence
N1 - Publisher Copyright:
© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
PY - 2019/2/11
Y1 - 2019/2/11
N2 - The syn and anti isomers of [Fe IV (O)(TMC)] 2+ (TMC=tetramethylcyclam) represent the first isolated pair of synthetic non-heme oxoiron(IV) complexes with identical ligand topology, differing only in the position of the oxo unit bound to the iron center. Both isomers have previously been characterized. Reported here is that the syn isomer [Fe IV (O syn )(TMC)(NCMe)] 2+ (2) converts into its anti form [Fe IV (O anti )(TMC)(NCMe)] 2+ (1) in MeCN, an isomerization facilitated by water and monitored most readily by 1 H NMR and Raman spectroscopy. Indeed, when H 2 18 O is introduced to 2, the nascent 1 becomes 18 O-labeled. These results provide compelling evidence for a mechanism involving direct binding of a water molecule trans to the oxo atom in 2 with subsequent oxo–hydroxo tautomerism for its incorporation as the oxo atom of 1. The nonplanar nature of the TMC supporting ligand makes this isomerization an irreversible transformation, unlike for their planar heme counterparts.
AB - The syn and anti isomers of [Fe IV (O)(TMC)] 2+ (TMC=tetramethylcyclam) represent the first isolated pair of synthetic non-heme oxoiron(IV) complexes with identical ligand topology, differing only in the position of the oxo unit bound to the iron center. Both isomers have previously been characterized. Reported here is that the syn isomer [Fe IV (O syn )(TMC)(NCMe)] 2+ (2) converts into its anti form [Fe IV (O anti )(TMC)(NCMe)] 2+ (1) in MeCN, an isomerization facilitated by water and monitored most readily by 1 H NMR and Raman spectroscopy. Indeed, when H 2 18 O is introduced to 2, the nascent 1 becomes 18 O-labeled. These results provide compelling evidence for a mechanism involving direct binding of a water molecule trans to the oxo atom in 2 with subsequent oxo–hydroxo tautomerism for its incorporation as the oxo atom of 1. The nonplanar nature of the TMC supporting ligand makes this isomerization an irreversible transformation, unlike for their planar heme counterparts.
KW - iron
KW - isomers
KW - macrocycles
KW - reaction mechanisms
KW - tautomerism
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U2 - 10.1002/anie.201811454
DO - 10.1002/anie.201811454
M3 - Article
C2 - 30556289
AN - SCOPUS:85060209545
SN - 1433-7851
VL - 58
SP - 1995
EP - 1999
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 7
ER -