Theoretical Study on the Structural-Function Relationship of Manganese(III)-Iodosylarene Adducts.
ABSTRACT: Metal-iodosylarene complexes have been recently viewed as a second oxidant alongside of the well-known high-valent metal-oxo species. Extensive efforts have been exerted to unveil the structure-function relationship of various metal-iodosylarene complexes. In the present manuscript, density functional theoretical calculations were employed to investigate such relationship of a specific manganese-iodosylbenzene complex [MnIII(TBDAP)(PhIO)(OH)]2+ (1). Our results fit the experimental observations and revealed new mechanistic findings. 1 acts as a stepwise 1e+1e oxidant in sulfoxidation reactions. Surprisingly, C-H bond activation of 9,10-dihydroanthracene (DHA) by 1 proceeds via a novel ionic hydride transfer/proton transfer (HT/PT) mechanism. As a comparison to 1, the electrophilicity of an iodosylbenzene monomer PhIO was investigated. PhIO performs concerted 2e-oxidations both in sulfoxidation and C-H activation. Hydroxylation of DHA by PhIO was found to proceed via a novel ionic and concerted proton-transfer/hydroxyl-rebound mechanism involving 2e-oxidation to form a transient carbonium species.
Project description:To develop advanced materials using metal complexes, it is better to prepare metal complexes contained in composite or hybrid films. To achieve this purpose, we synthesized ruthenium complexes with dihalogen-substituted benzendithiolate ligands, [(??-C?Me?)Ru(S?C?H?X?)] (X = F, 3,6-Cl, Br, 4,5-Cl), 1b-1e. We also investigated preparation of 1c or 1e containing polysiloxane composite films and their reactivity to CO gas. All ruthenium complexes 1b-1e reacted with CO gas, and carbonyl ligand adducts 2b-2e were generated. Ruthenium complexes 1b-1e show two strong absorption peaks around 550 and 420 nm. After exposure to CO gas, these absorption peaks were immediately decreased without a peak shift. A similar trend was observed in 1c or 1e containing polysiloxane composite films. These results indicate that 1c and 1e were easily converted into 2c and 2e, both in the solution and the polysiloxane film during CO gas exposure.
Project description:A mononuclear Cr(v)-oxo complex, [CrV(O)(6-COO--tpa)](BF4)2 (1; 6-COO--tpa = N,N-bis(2-pyridylmethyl)-N-(6-carboxylato-2-pyridylmethyl)amine) was prepared through the reaction of a Cr(iii) precursor complex with iodosylbenzene as an oxidant. Characterization of 1 was achieved using ESI-MS spectrometry, electron paramagnetic resonance, UV-vis, and resonance Raman spectroscopies. The reduction potential (Ered) of 1 was determined to be 1.23 V vs. SCE in acetonitrile based on analysis of the electron-transfer (ET) equilibrium between 1 and a one-electron donor, [RuII(bpy)3]2+ (bpy = 2,2'-bipyridine). The reorganization energy (?) of 1 was also determined to be 1.03 eV in ET reactions from phenol derivatives to 1 on the basis of the Marcus theory of ET. The smaller ? value in comparison with that of an Fe(iv)-oxo complex (2.37 eV) is caused by the small structural change during ET due to the d? character of the electron-accepting LUMO of 1. When benzyl alcohol derivatives (R-BA) with different oxidation potentials were employed as substrates, corresponding aldehydes were obtained as the 2e--oxidized products in moderate yields as determined from 1H NMR and GC-MS measurements. One-step UV-vis spectral changes were observed in the course of the oxidation reactions of BA derivatives by 1 and a kinetic isotope effect (KIE) was observed in the oxidation reactions for deuterated BA derivatives at the benzylic position as substrates. These results indicate that the rate-limiting step is a concerted proton-coupled electron transfer (PCET) from substrate to 1. In sharp contrast, in the oxidation of trimethoxy-BA (Eox = 1.22 V) by 1, trimethoxy-BA radical cation was observed by UV-vis spectroscopy. Thus, it was revealed that the mechanism of the oxidation reaction changed from one-step PCET to stepwise ET-proton transfer (ET/PT), depending on the redox potentials of R-BA.
Project description:We report the latent production of free radicals from energy stored in a redox potential through a 2e(-)/1H(+) transfer process, analogous to energy harvesting in photosynthesis, using visible-light organic photoredox catalysis (photocatalysis) of methylene blue chromophore with a sacrificial sterically hindered amine reductant and an onium salt oxidant. This enables light-initiated free-radical polymerization to continue over extended time intervals (hours) in the dark after brief (seconds) low-intensity illumination and beyond the spatial reach of light by diffusion of the metastable leuco-methylene blue photoproduct. The present organic photoredox catalysis system functions via a 2e(-)/1H(+) shuttle mechanism, as opposed to the 1e(-) transfer process typical of organometallic-based and conventional organic multicomponent photoinitiator formulations. This prevents immediate formation of open-shell (radical) intermediates from the amine upon light absorption and enables the "storage" of light-energy without spontaneous initiation of the polymerization. Latent energy release and radical production are then controlled by the subsequent light-independent reaction (analogous to the Calvin cycle) between leuco-methylene blue and the onium salt oxidant that is responsible for regeneration of the organic methylene blue photocatalyst. This robust approach for photocatalysis-based energy harvesting and extended release in the dark enables temporally controlled redox initiation of polymer syntheses under low-intensity short exposure conditions and permits visible-light-mediated synthesis of polymers at least 1 order of magnitude thicker than achievable with conventional photoinitiated formulations and irradiation regimes.
Project description:Dioxygen addition to coordinatively unsaturated [Fe(II)(O(Me2)N4(6-Me-DPEN))](PF6) (1) is shown to afford a complex containing a dihydroxo-bridged Fe(III)2(?-OH)2 diamond core, [Fe(III)(O(Me2)N4(6-Me-DPEN))]2(?-OH)2(PF6)2·(CH3CH2CN)2 (2). The diamond core of 2 resembles the oxidized methane monooxygenase (MMOox) resting state, as well as the active site product formed following H-atom abstraction from Tyr-OH by ribonucleotide reductase (RNR). The Fe-OH bond lengths of 2 are comparable with those of the MMOHox suggesting that MMOHox contains a Fe(III)2(?-OH)2 as opposed to Fe(III)2(?-OH)(?-OH2) diamond core as had been suggested. Isotopic labeling experiments with (18)O2 and CD3CN indicate that the oxygen and proton of the ?-OH bridges of 2 are derived from dioxygen and acetonitrile. Deuterium incorporation (from CD3CN) suggests that an unobserved intermediate capable of abstracting a H-atom from CH3CN forms en route to 2. Given the high C-H bond dissociation energy (BDE = 97 kcal/mol) of acetonitrile, this indicates that this intermediate is a potent oxidant, possibly a high-valent iron oxo. Consistent with this, iodosylbenzene (PhIO) also reacts with 1 in CD3CN to afford the deuterated Fe(III)2(?-OD)2 derivative of 2. Intermediates are not spectroscopically observed in either reaction (O2 and PhIO) even at low-temperatures (-80 °C), indicating that this intermediate has a very short lifetime, likely due to its highly reactive nature. Hydroxo-bridged 2 was found to stoichiometrically abstract hydrogen atoms from 9,10-dihydroanthracene (C-H BDE = 76 kcal/mol) at ambient temperatures.
Project description:Despite the significant progress, C-H arylation with aryldiazonium salts is a major challenge because of the faster rate of oxidative addition compared to the C-H insertion, leading to a deleterious homocoupling product. Recently, this limitation has been overcome by merging a photoredox catalyst with transition-metal catalysts which proceeds through a distinct single electron-transfer mechanism. However, we have observed that the photoredox catalyst is not necessary for the C-H arylation of aniline rather chemical reactivity can be controlled by tuning the electronic nature of the substrate. We report, herein, a palladium-catalyzed C-H arylation of aniline carbamates with aryldiazonium salts under external oxidant, acid, base free conditions at room temperature. Mechanistic studies suggest that the present reaction proceeds through a directed electrophilic metalation pathway which is the slowest step. However, the oxidative addition may take place through either ionic (2e-) or radical (1e-) pathway to generate hypervalent Pd(IV) or Pd(III) intermediate, respectively. A facile reductive elimination from the hypervalent palladium complex furnishes the C-H arylation product under mild conditions. The carbamate directing group is easily removed from the product to obtain the corresponding ortho-arylated aniline, which is a precursor for plethora of carbazole alkaloids and other biologically active molecules. The reaction is scaled-up to gram scale to furnish the desired product in comparable yields. Finally, we have applied this C-H arylation methodology for the synthesis of series of carbazole alkaloids such as clausine V, clauszoline K, O-methoxymahanine, and O-methylmurrayamine-D.
Project description:We report the synthesis, characterization, and reactivity of [LFe3 (PhPz)3 OMn(s PhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (FeIII2 FeII MnII vs. FeIII3 MnII ) influence oxygen atom transfer in tetranuclear Fe3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.
Project description:Oxidation and reduction events are critical to physiological and pathological processes and are highly regulated. Herein, we present evidence for the role of Ras and Rho GTPases in controlling these events and the unique underlying mechanisms. Evidence for redox regulation of Ras GTPases that contain a redox-sensitive cysteine (X) in the conserved NKXD motif is presented, and a growing consensus supports regulation by a thiyl radical-mediated oxidation mechanism. We also discuss the debate within the literature regarding whether 2e(-) oxidation mechanisms also regulate Ras GTPase activity.We examine the increasing in vitro and cell-based data supporting oxidant-mediated activation of Rho GTPases that contain a redox-sensitive cysteine at the end of the conserved phosphoryl-binding loop (p-loop) motif (GXXXXG[S/T]C). While this motif is distinct from Ras, these data suggest a similar 1e(-) oxidation-mediated activation mechanism.We also review the data showing that the unique p-loop placement of the redox-sensitive cysteine in Rho GTPases supports activation by 2e(-) cysteine oxidation. Finally, we examine the role that Ras and Rho GTPases play in controlling key oxidant-regulating enzymes in the cell, and we speculate on a feedback mechanism.Given that these GTPases and redox-regulating enzymes are involved in multiple physiological and pathological processes, we discuss future experiments that may clarify the interplay between them.
Project description:We employed an analytical approach to evaluate the key parameters for the potential design optimisation of accommodating intra-ocular lenses (AIOL) and to use these parameters to predict their accommodative performance.Paraxial thin-lens equations to predict the accommodative performances of single-element (1E) and two-element (2E) AIOLs were developed. 2E-AIOLs with either mobile front or back lens elements were analysed as well as 1E-AIOL for their accommodative performance. A paraxial model including key ocular components (corneal surfaces, pupil and retina) as well as AIOL was used to evaluate the key control parameters and optimal design configurations. A range of variants of the model, representing varying powers of front and back optical elements and with either front or back optical element mobile was tested.Optimal accommodative performance of 2E-AIOL is governed by the power combinations of its optical elements; design variants with higher positive front element power produced greater accommodative efficacy, while mobility of the front element contributed more to the accommodative performance than the back element. The performance of 1E-AIOL is primarily governed by the power of the AIOL; the higher the AIOL power, the better the accommodative performance.From an accommodative performance standpoint, the optimal design of 2E-AIOL should comprise a high plus power front element. Considering the maximum potential amounts of element translation available clinically, 2E-AIOLs are predicted to offer higher accommodative performance compared to 1E-AIOL.
Project description:The number of electrons in small metallic or semiconducting islands is quantised. When tunnelling is enabled via opaque barriers this number can change by an integer. In superconductors the addition is in units of two electron charges (2e), reflecting that the Cooper pair condensate must have an even parity. This ground state (GS) is foundational for all superconducting qubit devices. Here, we study a hybrid superconducting-semiconducting island and find three typical GS evolutions in a parallel magnetic field: a robust 2e-periodic even-parity GS, a transition to a 2e-periodic odd-parity GS, and a transition from a 2e- to a 1e-periodic GS. The 2e-periodic odd-parity GS persistent in gate-voltage occurs when a spin-resolved subgap state crosses zero energy. For our 1e-periodic GSs we explicitly show the origin being a single zero-energy state gapped from the continuum, i.e., compatible with an Andreev bound states stabilized at zero energy or the presence of Majorana zero modes.
Project description:Galactose oxidase (GO) is a copper-dependent enzyme that accomplishes 2e- substrate oxidation by pairing a single copper with an unusual cysteinylated tyrosine (Cys-Tyr) redox cofactor. Previous studies have demonstrated that the post-translational biogenesis of Cys-Tyr is copper- and O2-dependent, resulting in a self-processing enzyme system. To investigate the mechanism of cofactor biogenesis in GO, the active-site structure of Cu(I)-loaded GO was determined using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy, and density-functional theory (DFT) calculations were performed on this model. Our results show that the active-site tyrosine lowers the Cu potential to enable the thermodynamically unfavorable 1e- reduction of O2, and the resulting Cu(II)-O2•- is activated toward H atom abstraction from cysteine. The final step of biogenesis is a concerted reaction involving coordinated Tyr ring deprotonation where Cu(II) coordination enables formation of the Cys-Tyr cross-link. These spectroscopic and computational results highlight the role of the Cu(I) in enabling O2 activation by 1e- and the role of the resulting Cu(II) in enabling substrate activation for biogenesis.