Redox-inactive ions control the redox-activity of molecular vanadium oxides.

Polyoxometalates are key materials for energy conversion and storage due to their unique chemical tunability and electrochemical reactivity. Herein, we report that functionalization of molecular vanadium oxides, polyoxovanadates, with redox-inert Ca2+ cations leads to a significant increase in their electron storage capabilities. The electrochemical performance of the Ca2+-functionalized dodecavanadate [Ca2V12O32Cl(DMF)3]2- (={Ca 2 V 12 }) was thus compared with that of the precursor compound (H2NMe2)2[V12O32Cl]3- (={V 12 }). {Ca 2 V 12 } can store up to five electrons per cluster, while {V 12 } only shows one reversible redox transition. In initial studies, we demonstrated that {Ca 2 V 12 } can be used as an active material in lithium-ion cathodes. Our results show how redox-inert cations can be used as structural and electrostatic stabilizers, leading to major changes in the redox-chemistry of polyoxovanadates.

Solvent-Controlled Polymerization of Molecular Strontium Vanadate Monomers into 1D Strontium Vanadium Oxide Chains.

We report the polymerization of a solvent-stabilized molecular strontium vanadium oxide monomer into infinite 1D chains. Supramolecular polymerization is triggered by controlled solvent-exchange, which leads to oligomer and polymer formation. Mechanistic insights into the chain formation were obtained by solid-state, solution, and gas-phase studies. The study shows how reactivity control of molecular metal oxides can be used to assemble complex inorganic polymeric structures.

Synthesis and structural characterisation of unprecedented primary N-nitrosamines coordinated to iridium(iv).

The redox chemistry of the N-nitrosamine complexes [IrCl5(RN(H)N[double bond, length as m-dash]O)]2- (R = benzyl or n-butyl) was studied in detail. One-electron oxidations at around 200 mV vs. ferrocene/ferrocenium were reversible in cyclic voltammograms. UV-vis spectroelectrochemistry reveals spectra characteristic of IrIV species but also partial decomposition of the oxidised species [IrIVCl5(RN(H)N[double bond, length as m-dash]O)]˙- on this timescale (minutes). Detailed studies on chemically oxidised solutions of the parent IrIII complexes gave evidence for paramagnetic IrIV from NMR spectra. Final products of the decomposition were the corresponding alcohols and presumably [IrIIICl5(L)]2- (L = N2, solvent, amine) complexes. Similar decomposition reactions of acidic DMSO solutions of [IrCl5(RN(H)N[double bond, length as m-dash]O)]2-revealed that this combination produces the so-called "activated" DMSO (Me2S+-O- or Me2S+-OE, with "E" being an electrophile) which oxidises the parent IrIII complexes. Finally, with the very reactive purple IrIV compound (PPh4)[IrCl5(BnN(H)N[double bond, length as m-dash]O)], the first primary N-nitrosamine coordinated to [IrIVCl5]- was isolated and characterised by UV-vis absorption, FTIR, NMR spectroscopy, ultra-high resolution electrospray mass spectrometry (UHR-ESI-MS) and iridium L3 X-ray absorption near-edge spectroscopy (XANES).

Redox Behavior of a Dinuclear Ruthenium(II) Complex Bearing an Uncommon Bridging Ligand: Insights from High-Pressure Electrochemistry.

A dinuclear ruthenium complex bridged by 2,3,5,6-pyrazinetetracarboxylic acid (µ-LH22-) was synthesized and characterized by X-ray crystallography, cyclic voltammetry under ambient and elevated pressures, electron paramagnetic resonance (EPR) and UV/vis-NIR (NIR = near-infrared) spectroelectrochemistry, pulse radiolysis, and computational methods. We probed for the first time in the field of mixed-valency the use of high-pressure electrochemical methods. The investigations were directed toward the influence of the protonation state of the bridging ligand on the electronic communication between the ruthenium ions, since such behavior is interesting in terms of modulating redox chemistry by pH. Starting from the [RuII(µ-LH22-)RuII]0 configuration, which shows an intense metal-to-ligand charge transfer absorption band at 600 nm, cyclic voltammetry revealed a pH-independent, reversible one-electron reduction and a protonation-state-dependent (proton coupled electron transfer, PCET) reversible oxidation. Deeper insight into the electrode reactions was provided by pressure-dependent cyclic voltammetry up to 150 MPa, providing insight into the conformational changes, the protonation state, and the environment of the molecule during the redox processes. Spectroelectrochemical investigations (EPR, UV/vis-NIR) of the respective redox reactions suggest a ligand-centered radical anion [RuII(µ-LH2•3-)RuII]- upon reduction (EPR Δg = 0.042) and an ambiguous, EPR-silent one-electron oxidized state. In both cases, the absence of the otherwise typical broad intervalence charge transfer bands in the NIR region for mixed-valent complexes support the formulation as radical anionic bridged compound. However, on the basis of high-pressure electrochemical data and density functional theory calculations the one-electron oxidized form could be assigned as a charge-delocalized [RuII.5(µ-LH22-)RuII.5]+ valence tautomer rather than [RuIII(µ-LH2•3-)RuIII]+. Deprotonation of the bridging ligand causes a severe shift of the redox potential for the metal-based oxidation toward lower potentials, yielding the charge-localized [RuIII(µ-LH3-)RuII]0 complex. This PCET process is accompanied by large intrinsic volume changes. All findings are supported by computational methods (geometry optimization, spin population analysis). For all redox processes, valence alternatives are discussed.

Record Broken: A Copper Peroxide Complex with Enhanced Stability and Faster Hydroxylation Catalysis.

Tyrosinase model systems pinpoint pathways to translating Nature's synthetic abilities for useful synthetic catalysts. Mostly, they use N-donor ligands which mimic the histidine residues coordinating the two copper centres. Copper complexes with bis(pyrazolyl)methanes with pyridinyl or imidazolyl moieties are already reported as excellent tyrosinase models. Substitution of the pyridinyl donor results in the new ligand HC(3-tBuPz)2 (4-CO2 MePy) which stabilises a room-temperature stable µ-η2 :η2 -peroxide dicopper(II) species upon oxygenation. It reveals highly efficient catalytic activity as it hydroxylates 8-hydroxyquinoline in high yields (TONs of up to 20) and much faster than all other model systems (max. conversion within 7.5 min). Stoichiometric reactions with para-substituted sodium phenolates show saturation kinetics which are nearly linear for electron-rich substrates. The resulting Hammett correlation proves the electrophilic aromatic substitution mechanism. Furthermore, density functional theory (DFT) calculations elucidate the influence of the substituent at the pyridinyl donor: the carboxymethyl group adjusts the basicity and nucleophilicity without additional steric demand. This substitution opens up new pathways in reactivity tuning.

Switching between Inner- and Outer-Sphere PCET Mechanisms of Small-Molecule Activation: Superoxide Dismutation and Oxygen/Superoxide Reduction Reactivity Deriving from the Same Manganese Complex.

Readily exchangeable water molecules are commonly found in the active sites of oxidoreductases, yet the overwhelming majority of studies on small-molecule mimics of these enzymes entirely ignores the contribution of water to the reactivity. Studies of how these enzymes can continue to function in spite of the presence of highly oxidizing species are likewise limited. The mononuclear MnII complex with the potentially hexadentate ligand N-(2-hydroxy-5-methylbenzyl)-N,N',N'-tris(2-pyridinylmethyl)-1,2-ethanediamine (LOH) was previously found to act as both a H2O2-responsive MRI contrast agent and a mimic of superoxide dismutase (SOD). Here, we studied this complex in aqueous solutions at different pH values in order to determine its (i) acid-base equilibria, (ii) coordination equilibria, (iii) substitution lability and operative mechanisms for water exchange, (iv) redox behavior and ability to participate in proton-coupled electron transfer (PCET) reactions, (v) SOD activity and reductive activity toward both oxygen and superoxide, and (vi) mechanism for its transformation into the binuclear MnII complex with (H)OL-LOH and its hydroxylated derivatives. The conclusions drawn from potentiometric titrations, low-temperature mass spectrometry, temperature- and pressure-dependent 17O NMR spectroscopy, electrochemistry, stopped-flow kinetic analyses, and EPR measurements were supported by the structural characterization and quantum chemical analysis of proposed intermediate species. These comprehensive studies enabled us to determine how transiently bound water molecules impact the rate and mechanism of SOD catalysis. Metal-bound water molecules facilitate the PCET necessary for outer-sphere SOD activity. The absence of the water ligand, conversely, enables the inner-sphere reduction of both superoxide and dioxygen. The LOH complex maintains its SOD activity in the presence of •OH and MnIV-oxo species by channeling these oxidants toward the synthesis of a functionally equivalent binuclear MnII species.

Aromatic C-F Hydroxylation by Nonheme Iron(IV)-Oxo Complexes: Structural, Spectroscopic, and Mechanistic Investigations.

The synthesis and reactivity of a series of mononuclear nonheme iron complexes that carry out intramolecular aromatic C-F hydroxylation reactions is reported. The key intermediate prior to C-F hydroxylation, [FeIV(O)(N4Py2Ar1)](BF4)2 (1-O, Ar1 = -2,6-difluorophenyl), was characterized by single-crystal X-ray diffraction. The crystal structure revealed a nonbonding C-H···O═Fe interaction with a CH3CN molecule. Variable-field Mössbauer spectroscopy of 1-O indicates an intermediate-spin (S = 1) ground state. The Mössbauer parameters for 1-O include an unusually small quadrupole splitting for a triplet FeIV(O) and are reproduced well by density functional theory calculations. With the aim of investigating the initial step for C-F hydroxylation, two new ligands were synthesized, N4Py2Ar2 (L2, Ar2 = -2,6-difluoro-4-methoxyphenyl) and N4Py2Ar3 (L3, Ar3 = -2,6-difluoro-3-methoxyphenyl), with -OMe substituents in the meta or ortho/para positions with respect to the C-F bonds. FeII complexes [Fe(N4Py2Ar2)(CH3CN)](ClO4)2 (2) and [Fe(N4Py2Ar3)(CH3CN)](ClO4)2 (3) reacted with isopropyl 2-iodoxybenzoate to give the C-F hydroxylated FeIII-OAr products. The FeIV(O) intermediates 2-O and 3-O were trapped at low temperature and characterized. Complex 2-O displayed a C-F hydroxylation rate similar to that of 1-O. In contrast, the kinetics (via stopped-flow UV-vis) for complex 3-O displayed a significant rate enhancement for C-F hydroxylation. Eyring analysis revealed the activation barriers for the C-F hydroxylation reaction for the three complexes, consistent with the observed difference in reactivity. A terminal FeII(OH) complex (4) was prepared independently to investigate the possibility of a nucleophilic aromatic substitution pathway, but the stability of 4 rules out this mechanism. Taken together the data fully support an electrophilic C-F hydroxylation mechanism.

Copper Chloride Catalysis: Do µ4-Oxido Copper Clusters Play a Significant Role?

Copper chloride catalysis is a well-established field in organic and inorganic chemistry. However, in most cases a detailed mechanistic understanding of the individual reaction steps and identification of reactive intermediates are still missing. The present study reports the results of spectroscopic and spectrometric measurements that support formation of copper agglomerates during catalytic processes. The composition of CuCl2·2H2O in several coordinating solvents and the influence of basic coreagents such as NaO(t)Bu and K2CO3 on the structure in the solid state as well as in solution were investigated. Several experiments involving crystal structure determination, IR spectroscopy, and ultra-high-resolution cryospray-ionization mass spectrometry were performed. The crystal structures of [CuCl2(H2O)]·0.5(CH3)2CO (1), [Cu2(CH3CN)2Cl4] (2), [Cu3(CH3CN)3Cl6] (3), [Cu3Cl6(THF)4] (4), [Cu(DMSO)2Cl2] (5), (H2N(CH3)2)2[CuCl3] (6), and [Cu4OCl6(THF)(urea)3]·3THF·urea (8) are reported herein. It can be clearly demonstrated that µ4-oxido copper clusters of the formula [Cu4OCl6(solvent)4] are the main product from the reactions of CuCl2·2H2O and basic coreagents. As a final result of these experiments, it can be stated that µ4-oxido copper clusters most likely play an important role in the mechanism of copper chloride-catalyzed reactions.

Photoinitiated Reactivity of a Thiolate-Ligated, Spin-Crossover Nonheme {FeNO}(7) Complex with Dioxygen.

The nonheme iron complex, [Fe(NO)(N3PyS)]BF4, is a rare example of an {FeNO}(7) species that exhibits spin-crossover behavior. The comparison of X-ray crystallographic studies at low and high temperatures and variable-temperature magnetic susceptibility measurements show that a low-spin S = 1/2 ground state is populated at 0-150 K, while both low-spin S = 1/2 and high-spin S = 3/2 states are populated at T > 150 K. These results explain the observation of two N-O vibrational modes at 1737 and 1649 cm(-1) in CD3CN for [Fe(NO)(N3PyS)]BF4 at room temperature. This {FeNO}(7) complex reacts with dioxygen upon photoirradiation with visible light in acetonitrile to generate a thiolate-ligated, nonheme iron(III)-nitro complex, [Fe(III)(NO2)(N3PyS)](+), which was characterized by EPR, FTIR, UV-vis, and CSI-MS. Isotope labeling studies, coupled with FTIR and CSI-MS, show that one O atom from O2 is incorporated in the Fe(III)-NO2 product. The O2 reactivity of [Fe(NO)(N3PyS)]BF4 in methanol is dramatically different from CH3CN, leading exclusively to sulfur-based oxidation, as opposed to NO· oxidation. A mechanism is proposed for the NO· oxidation reaction that involves formation of both Fe(III)-superoxo and Fe(III)-peroxynitrite intermediates and takes into account the experimental observations. The stability of the Fe(III)-nitrite complex is limited, and decay of [Fe(III)(NO2)(N3PyS)](+) leads to {FeNO}(7) species and sulfur oxygenated products. This work demonstrates that a single mononuclear, thiolate-ligated nonheme {FeNO}(7) complex can exhibit reactivity related to both nitric oxide dioxygenase (NOD) and nitrite reductase (NiR) activity. The presence of the thiolate donor is critical to both pathways, and mechanistic insights into these biologically relevant processes are presented.

Discovery and Characterization of Biased Allosteric Agonists of the Chemokine Receptor CXCR3.

In this work we report a design, synthesis, and detailed functional characterization of unique strongly biased allosteric agonists of CXCR3 that contain tetrahydroisoquinoline carboxamide cores. Compound 11 (FAUC1036) is the first strongly biased allosteric agonist of CXCR3 that selectively induces weak chemotaxis and leads to receptor internalization and the ß-arrestin 2 recruitment with potency comparable to that of the chemokine CXCL11 without any activation of G proteins. A subtle structural change (addition of a methoxy group, 14 (FAUC1104)) led to a contrasting biased allosteric partial agonist that activated solely G proteins, induced chemotaxis, but failed to induce receptor internalization or ß-arrestin 2 recruitment. Concomitant structure-activity relationship studies indicated very steep structure-activity relationships, which steer the ligand bias between the ß-arrestin 2 and G protein pathway. Overall, the information presented provides a powerful platform for further development and rational design of strongly biased allosteric agonists of CXCR3.

Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions.

Tuning reagent and catalyst concentrations is crucial in the development of efficient catalytic transformations. In enzyme-catalysed reactions the substrate is bound-often by multiple non-covalent interactions-in a well-defined pocket close to the active site of the enzyme; this pre-organization facilitates highly efficient transformations. Here we report an artificial system that co-encapsulates multiple catalysts and substrates within the confined space defined by an M12L24 nanosphere that contains 24 endohedral guanidinium-binding sites. Cooperative binding means that sulfonate guests are bound much more strongly than carboxylates. This difference has been used to fix gold-based catalysts firmly, with the remaining binding sites left to pre-organize substrates. This strategy was applied to a Au(I)-catalysed cyclization of acetylenic acid to enol lactone in which the pre-organization resulted in much higher reaction rates. We also found that the encapsulated sulfonate-containing Au(I) catalysts did not convert neutral (acid) substrates, and so could have potential in the development of substrate-selective catalysis and base-triggered on/off switching of catalysis.

Halide coordinated homoleptic [Fe4S4X4](2-) and heteroleptic [Fe4S4X2Y2](2-) clusters (X, Y = Cl, Br, I)--alternative preparations, structural analogies and spectroscopic properties in solution and solid state.

New facile methods to prepare iron sulphur halide clusters [Fe4S4X4](2-) from [Fe(CO)5] and elemental sulphur were elaborated. Reactions of ferrous precursors like tetrahalidoferrates(ii) or simple ferrous halides with [Fe(CO)5] and sulphur turned out to be efficient methods to prepare homoleptic [Fe4S4X4](2-) (X = Cl, Br) and heteroleptic clusters [Fe4S4X4-nYn](2-) (X = Cl, Br; Y = Br, I). Solid materials were obtained as salts of BTMA(+) (= benzyltrimethylammonium); the new compounds containing [Fe4S4Br4](2-) and [Fe4S4X2Y2](2-) (X, Y = Cl, Br, I) were all isostructural to (BTMA)2[Fe4S4I4] (monoclinic, Cc) as inferred from synchrotron X-ray powder diffraction. While the solid materials contain defined heteroleptic clusters with a halide X : Y ratio of 2 : 2, dissolving these compounds leads to rapid scrambling of the halide ligands forming mixtures of all five possible [Fe4S4X4-nYn](2-) clusters as could be shown by UHR-ESI MS. The variation of X and Y allowed assignment of the absorption bands in the visible and NIR; the long-wavelength bands around 1100 nm were tentatively assigned to intervalence charge transfer (IVCT) transitions.

Aggregation of a Crown Ether Decorated Zinc-Phthalocyanine by Collision-Induced Desolvation of Electrospray Droplets.

The aggregation of phthalocyanines is well-known in solution but has never before been studied in the gas phase. We investigated the tetra-[18]crown-6 ether functionalized zinc-phthalocyanine (ZnPcTetCr, M) with electrospray ionization mass spectrometry (ESI-MS) in the absence of coordinating metal cations. Apart from the molecular ion M(+•), singly and multiply charged aggregates Mn(z(+•)) were observed, bound together by electrostatic interactions, without alkali metal cations inside the crown ethers. Collision-induced dissociation (CID) experiments indicate that these clusters consist of stacked neutral M and radical cations M(+•). After the oxidation of individual molecules at the electrospray needle, the aggregation occurs during desolvation of the charged droplets created in the source. Complete evaporation of the solvent and detection of the aggregates was found to require an additional acceleration of the droplets in the transfer region of the instrument, the resulting collisions with neutral gas assisting the desolvation process.

Efficient Biomimetic Hydroxylation Catalysis with a Bis(pyrazolyl)imidazolylmethane Copper Peroxide Complex.

Bis(pyrazolyl)methane ligands are excellent components of model complexes used to investigate the activity of the enzyme tyrosinase. Combining the N donors 3-tert-butylpyrazole and 1-methylimidazole results in a ligand that is capable of stabilising a (µ-η(2) :η(2) )-dicopper(II) core that resembles the active centre of tyrosinase. UV/Vis spectroscopy shows blueshifted UV bands in comparison to other known peroxo complexes, due to donor competition from different ligand substituents. This effect was investigated with the help of theoretical calculations, including DFT and natural transition orbital analysis. The peroxo complex acts as a catalyst capable of hydroxylating a variety of phenols by using oxygen. Catalytic conversion with the non-biological phenolic substrate 8-hydroxyquinoline resulted in remarkable turnover numbers. In stoichiometric reactions, substrate-binding kinetics was observed and the intrinsic hydroxylation constant, kox , was determined for five phenolates. It was found to be the fastest hydroxylation model system determined so far, reaching almost biological activity. Furthermore, Hammett analysis proved the electrophilic character of the reaction. This sheds light on the subtle role of donor strength and its influence on hydroxylation activity.

Does perthionitrite (SSNO(-)) account for sustained bioactivity of NO? A (bio)chemical characterization.

Hydrogen sulfide (H2S) and nitric oxide (NO) are important signaling molecules that regulate several physiological functions. Understanding the chemistry behind their interplay is important for explaining these functions. The reaction of H2S with S-nitrosothiols to form the smallest S-nitrosothiol, thionitrous acid (HSNO), is one example of physiologically relevant cross-talk between H2S and nitrogen species. Perthionitrite (SSNO(-)) has recently been considered as an important biological source of NO that is far more stable and longer living than HSNO. In order to experimentally address this issue here, we prepared SSNO(-) by two different approaches, which lead to two distinct species: SSNO(-) and dithionitric acid [HON(S)S/HSN(O)S]. (H)S2NO species and their reactivity were studied by (15)N NMR, IR, electron paramagnetic resonance and high-resolution electrospray ionization time-of-flight mass spectrometry, as well as by X-ray structure analysis and cyclic voltammetry. The obtained results pointed toward the inherent instability of SSNO(-) in water solutions. SSNO(-) decomposed readily in the presence of light, water, or acid, with concomitant formation of elemental sulfur and HNO. Furthermore, SSNO(-) reacted with H2S to generate HSNO. Computational studies on (H)SSNO provided additional explanations for its instability. Thus, on the basis of our data, it seems to be less probable that SSNO(-) can serve as a signaling molecule and biological source of NO. SSNO(-) salts could, however, be used as fast generators of HNO in water solutions.

Nitrogen Oxide Atom-Transfer Redox Chemistry; Mechanism of NO(g) to Nitrite Conversion Utilizing µ-oxo Heme-Fe(III)-O-Cu(II)(L) Constructs.

While nitric oxide (NO, nitrogen monoxide) is a critically important signaling agent, its cellular concentrations must be tightly controlled, generally through its oxidative conversion to nitrite (NO2(-)) where it is held in reserve to be reconverted as needed. In part, this reaction is mediated by the binuclear heme a3/CuB active site of cytochrome c oxidase. In this report, the oxidation of NO(g) to nitrite is shown to occur efficiently in new synthetic µ-oxo heme-Fe(III)-O-Cu(II)(L) constructs (L being a tridentate or tetradentate pyridyl/alkylamino ligand), and spectroscopic and kinetic investigations provide detailed mechanistic insights. Two new X-ray structures of µ-oxo complexes have been determined and compared to literature analogs. All µ-oxo complexes react with 2 mol equiv NO(g) to give 1:1 mixtures of discrete [(L)Cu(II)(NO2(-))](+) plus ferrous heme-nitrosyl compounds; when the first NO(g) equiv reduces the heme center and itself is oxidized to nitrite, the second equiv of NO(g) traps the ferrous heme thus formed. For one µ-oxo heme-Fe(III)-O-Cu(II)(L) compound, the reaction with NO(g) reveals an intermediate species ("intermediate"), formally a bis-NO adduct, [(NO)(porphyrinate)Fe(II)-(NO2(-))-Cu(II)(L)](+) (λmax = 433 nm), confirmed by cryo-spray ionization mass spectrometry and EPR spectroscopy, along with the observation that cooling a 1:1 mixture of [(L)Cu(II)(NO2(-))](+) and heme-Fe(II)(NO) to -125 °C leads to association and generation of the key 433 nm UV-vis feature. Kinetic-thermodynamic parameters obtained from low-temperature stopped-flow measurements are in excellent agreement with DFT calculations carried out which describe the sequential addition of NO(g) to the µ-oxo complex.

Direct observation of a nonheme iron(IV)-oxo complex that mediates aromatic C-F hydroxylation.

The synthesis of a pentadentate ligand with strategically designed fluorinated arene groups in the second coordination sphere of a nonheme iron center is reported. The oxidatively resistant fluorine substituents allow for the trapping and characterization of an Fe(IV)(O) complex at -20 °C. Upon warming of the Fe(IV)(O) complex, an unprecedented arene C-F hydroxylation reaction occurs. Computational studies support the finding that substrate orientation is a critical factor in the observed reactivity. This work not only gives rare direct evidence for the participation of an Fe(IV)(O) species in arene hydroxylation but also provides the first example of a high-valent iron-oxo complex that mediates aromatic C-F hydroxylation.

Gold(I) catalysis at extreme concentrations inside self-assembled nanospheres.

Homogeneous transition-metal catalysis is a crucial technology for the sustainable preparation of valuable chemicals. The catalyst concentration is usually kept as low as possible, typically at mM or µM levels, and the effect of high catalyst concentration is hardly exploited because of solubility issues and the inherent unfavorable catalyst/substrate ratio. Herein, a self-assembly strategy is reported which leads to local catalyst concentrations ranging from 0.05 M to 1.1 M, inside well-defined nanospheres, whilst the overall catalyst concentration in solution remains at the conventional mM levels. We disclose that only at this high concentration, the gold(I) chloride is reactive and shows high selectivity in intramolecular CO and CC bond-forming cyclization reactions.

Activation of a high-valent manganese-oxo complex by a nonmetallic Lewis acid.

The reaction of a manganese(V)-oxo porphyrinoid complex with the Lewis acid B(C6F5)3 leads to reversible stabilization of the valence tautomer Mn(IV)(O)(π-radical cation). The latter complex, in combination with B(C6F5)3, reacts with ArO-H substrates via formal hydrogen-atom transfer and exhibits dramatically increased reaction rates over the Mn(V)(O) starting material.