Trapping of a phenoxyl radical at a non-haem high-spin iron(II) centre.

The activation of dioxygen at haem and non-haem metal centres, and subsequent functionalization of unactivated C‒H bonds, has been a focal point of much research. In iron-mediated oxidation reactions, O2 binding at an iron(II) centre is often accompanied by an oxidation of the iron centre. Here we demonstrate dioxygen activation by sodium tetraphenylborate and protons in the presence of an iron(II) complex to form a reactive radical species, whereby the iron oxidation state remains unaltered in the presence of a highly oxidizing phenoxyl radical and O2. This complex, containing an unusual iron(II)-phenoxyl radical motif, represents an elusive example of a spectroscopically characterized oxygen-derived iron(II)-reactive intermediate during chemical and biological dioxygen activation at haem and non-haem iron active centres. The present report opens up strategies for the stabilization of a phenoxyl radical cofactor, with its full oxidizing capabilities, to act as an independent redox centre next to an iron(II) site during substrate oxidation reactions.

Electronic Structure and Reactivity of Mononuclear Nonheme Iron-Peroxo Complexes as a Biomimetic Model of Rieske Oxygenases: Ring Size Effects of Macrocyclic Ligands.

We report the macrocyclic ring size-electronic structure-electrophilic reactivity correlation of mononuclear nonheme iron(III)-peroxo complexes bearing N-tetramethylated cyclam analogues (n-TMC), [FeIII(O2)(12-TMC)]+ (1), [FeIII(O2)(13-TMC)]+ (2), and [FeIII(O2)(14-TMC)]+ (3), as a model study of Rieske oxygenases. The Fe(III)-peroxo complexes show the same δ and pseudo-σ bonds between iron and the peroxo ligand. However, the strength of these interactions varies depending on the ring size of the n-TMC ligands; the overall Fe-O bond strength and the strength of the Fe-O2 δ bond increase gradually as the ring size of the n-TMC ligands becomes smaller, such as from 14-TMC to 13-TMC to 12-TMC. MCD spectroscopy plays a key role in assigning the characteristic low-energy δ → δ* LMCT band, which provides direct insight into the strength of the Fe-O2 δ bond and which, in turn, is correlated with the superoxo character of the iron-peroxo group. In oxidation reactions, reactivities of 1-3 toward hydrocarbon C-H bond activation are compared, revealing the reactivity order of 1 > 2 > 3; the [FeIII(O2)(n-TMC)]+ complex with a smaller n-TMC ring size, 12-TMC, is much more reactive than that with a larger n-TMC ring size, 14-TMC. DFT analysis shows that the Fe(III)-peroxo complex is not reactive toward C-H bonds, but it is the end-on Fe(II)-superoxo valence tautomer that is responsible for the observed reactivity. The hydrogen atom abstraction (HAA) reactivity of these intermediates is correlated with the overall donicity of the n-TMC ligand, which modulates the energy of the singly occupied π* superoxo frontier orbital that serves as the electron acceptor in the HAA reaction. The implications of these results for the mechanism of Rieske oxygenases are further discussed.

Preparation and Characterization of a Formally NiIV-Oxo Complex with a Triplet Ground State and Application in Oxidation Reactions.

High-valent first-row transition-metal-oxo complexes are important intermediates in biologically and chemically relevant oxidative transformations of organic molecules and in the water splitting reaction in (artificial) photosynthesis. While high-valent Fe- and Mn-oxo complexes have been characterized in detail, much less is known about their analogues with late transition metals. In this study, we present the synthesis and detailed characterization of a unique mononuclear terminal Ni-O complex. This compound, [Ni(TAML)(O)(OH)]3-, is characterized by an intense charge-transfer (CT) band around 730 nm and has an St = 1 ground state, as determined by magnetic circular dichroism spectroscopy. From extended X-ray absorption fine structure (EXAFS), the Ni-O bond distance is 1.84 Å. Ni K edge XAS data indicate that the complex contains a Ni(III) center, which results from an unusually large degree of Ni-O π-bond inversion, with one hole located on the oxo ligand. The complex is therefore best described as a low-spin Ni(III) complex (S = 1/2) with a bound oxyl (O•-) ligand (S = 1/2), where the spins of Ni and oxyl are ferromagnetically coupled, giving rise to the observed St = 1 ground state. This bonding description is roughly equivalent to the presence of a Ni-O single (σ) bond. Reactivity studies show that [Ni(TAML)(O)(OH)]3- is a strong oxidant capable of oxidizing thioanisole and styrene derivatives with large negative ρ values in the Hammett plot, indicating its electrophilic nature. The intermediate also shows high reactivity in C-H bond activation of hydrocarbons with a kinetic isotope effect of 7.0(3) in xanthene oxidation.

The Oxo-Wall Remains Intact: A Tetrahedrally Distorted Co(IV)-Oxo Complex.

In this paper, we report the preparation, spectroscopic and theoretical characterization, and reactivity studies of a Co(IV)-oxo complex bearing an N4-macrocyclic coligand, 12-TBC (12-TBC = 1,4,7,10-tetrabenzyl-1,4,7,10-tetraazacyclododecane). On the basis of the ligand and the structure of the Co(II) precursor, [CoII(12-TBC)(CF3SO3)2], one would assume that this species corresponds to a tetragonal Co(IV)-oxo complex, but the spectroscopic data do not support this notion. Co K-edge XAS data show that the treatment of the Co(II) precursor with iodosylbenzene (PhIO) as an oxidant at -40 °C in the presence of a proton source leads to a distinct shift in the Co K-edge, in agreement with the formation of a Co(IV) intermediate. The presence of the oxo group is further demonstrated by resonance Raman (rRaman) spectroscopy. Interestingly, the EPR data of this complex show a high degree of rhombicity, indicating structural distortion. This is further supported by the EXAFS data. Using DFT calculations, a structural model is developed for this complex with a ligand-protonated structure that features a Co═O···HN hydrogen bond and a four-coordinate Co center in a seesaw-shaped coordination geometry. Magnetic circular dichroism (MCD) spectroscopy further supports this finding. The hydrogen bond leads to an interesting polarization of the Co-oxo π-bonds, where one O(p) lone-pair is stabilized and leads to a regular Co(d) interaction, whereas the other π-bond shows an inverted ligand field. The reactivity of this complex in hydrogen atom and oxygen atom transfer reactions is discussed as well.

Iron and manganese oxo complexes, oxo wall and beyond.

High-valent metal-oxo species with multiply-bonded M-O groups have been proposed as key intermediates in many biological and abiological catalytic oxidation reactions. These intermediates are implicated as active oxidants in alkane hydroxylation, olefin epoxidation and other oxidation reactions. For example, [FeivO(porphyrinato•-)]+ cofactors bearing π-radical porphyrinato•- ligands oxidize organic substrates in cytochrome P450 enzymes, which are common to many life forms. Likewise, high-valent Mn-oxo species are active for H2O oxidation in photosystem II. The chemistry of these native reactive species has inspired chemists to prepare highly oxidized transition-metal complexes as functional mimics. Although many synthetic Fe-O and Mn-O complexes now exist, the analogous oxo complexes of the late transition metals (groups 9-11) are rare. Indeed, late-transition-metal-oxo complexes of tetragonal (fourfold) symmetry should be electronically unstable, a rule commonly referred to as the 'oxo wall'. A few late metal-oxos have been prepared by targeting other symmetries or unusual spin states. These complexes have been studied using spectroscopic and theoretical methods. This Review describes mononuclear non-haem Fe-O and Mn-O species, the nature of the oxo wall and recent advances in the preparation of oxo complexes of Co, Ni and Cu beyond the oxo wall.