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The hydroxylation of C–H bonds can be carried out by the high-valent CoIII,IV2(µ-O)2complex2asupported by the tetradentate tris(2-pyridylmethyl)amine ligand via a CoIII2(µ-O)(µ-OH) intermediate (3a). Complex3acan be independently generated either by H-atom transfer (HAT) in the reaction of2awith phenols as the H-atom donor or protonation of its conjugate base, the CoIII2(µ-O)2complex1a. Resonance Raman spectra of these three complexes reveal oxygen-isotope-sensitive vibrations at 560 to 590 cm−1associated with the symmetric Co–O–Co stretching mode of the Co2O2diamond core. Together with a Co•••Co distance of 2.78(2) Å previously identified for1aand2aby Extended X-ray Absorption Fine Structure (EXAFS) analysis, these results provide solid evidence for their “diamond core” structural assignments. The independent generation of3aallows us to investigate HAT reactions of2awith phenols in detail, measure the redox potential and pKaof the system, and calculate the O–H bond strength (DO–H) of3ato shed light on the C–H bond activation reactivity of2a. Complex3ais found to be able to transfer its hydroxyl ligand onto the trityl radical to form the hydroxylated product, representing a direct experimental observation of such a reaction by a dinuclear cobalt complex. Surprisingly, reactivity comparisons reveal2ato be 106-fold more reactive in oxidizing hydrocarbon C–H bonds than corresponding FeIII,IV2(µ-O)2and MnIII,IV2(µ-O)2analogs, an unexpected outcome that raises the prospects for using CoIII,IV2(µ-O)2species to oxidize alkane C–H bonds.
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Facile Conversion of syn ‐[Fe IV (O)(TMC)] 2+ into the anti Isomer via Meunier's Oxo–Hydroxo Tautomerism Mechanism
Abstract Thesynandantiisomers of [FeIV(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 thesynisomer [FeIV(Osyn)(TMC)(NCMe)]2+(2) converts into itsantiform [FeIV(Oanti)(TMC)(NCMe)]2+(1) in MeCN, an isomerization facilitated by water and monitored most readily by1H NMR and Raman spectroscopy. Indeed, when H218O is introduced to2, the nascent1becomes18O‐labeled. These results provide compelling evidence for a mechanism involving direct binding of a water moleculetransto the oxo atom in2with subsequent oxo–hydroxo tautomerism for its incorporation as the oxo atom of1. The nonplanar nature of the TMC supporting ligand makes this isomerization an irreversible transformation, unlike for their planar heme counterparts.
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- Award ID(s):
- 1665391
- PAR ID:
- 10083495
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 58
- Issue:
- 7
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 1995-1999
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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