Site-Independent Hydrogenation Reactions on Oxide-Supported Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion
Not Available
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Corrigendum: Balmer emission induced by proton impact on atomic hydrogen
In the original article [1] there is a misprint in the captions of figures 1 and 2. The AOCC calculations were labeled as (1) and the Glauber approximation as (2). It should be vice versa. In addition, in figure 2, the AOCC cross sections for excitation into the 3d1 and 3d2 states (dotted lines in panels (b) and (c)) were mistakenly reduced by a factor of 0.7. The correct results are shown below in the updated figure. Furthermore, these corrections do not affect the conclusions drawn in [1].
74 ATOMIC AND MOLECULAR PHYSICS↗
Hydrocyclization/Defluorination of CF 3 ‐Substituted Acrylamides: Insights from Kinetics of Hydrogen Atom Transfer
Abstract The introduction of F‐containing groups into organic molecules can significantly alter their physical and chemical properties. Particularly, gem ‐difluoroalkenes serve as versatile precursors for a broad variety of organofluorine compounds, commonly used in agrochemicals, pharmaceuticals, and materials science. Based on the kinetics of H• transfer to acrylamide ( k H = 2.28 × 10 −4 M −1 s −1 at 300 K in toluene), the study describes a nickel‐hydride‐(or Li[BEt 3 H]) initiated hydrocyclization/defluorination of CF 3 ‐substituted acrylamides, offering alternative access to 4‐fluorovinyl‐substituted 2‐pyrrolidones (Seletracetam derivatives that are antiepileptic drug candidates). This process proceeds with high yields and remarkable chemo‐ and regioselectivity. The hydrocyclization/defluorination can be initiated by either H• or H – transfer, followed by a 5‐exo‐trig cyclization and subsequent fluorine elimination. The strategy has been applied in the late‐stage functionalization of drug molecules, providing a valuable tool in the synthesis of pharmaceutical compounds.
Wan, Yanjun [College of Pharmaceutical Sciences Zh↗
Reactions of hydrazine with the amidogen radical and atomic hydrogen
The rate coefficient k 1 for NH 2 + N 2 H 4 was measured to be (5.4 ± 0.4) × 10 –14 cm 3 molecule –1 s –1 at 296 K. NH 2 was generated by pulsed laser photolysis of NH 3 at 193 nm, and monitored as a function of time by pulsed laser-induced fluorescence excited at 570.3 nm under pseudo-first order conditions in the presence of excess N 2 H 4 in an Ar bath gas. This reaction was also investigated computationally, with geometries and scaled frequencies obtained with M06-2X/6-311+G(2df,2p) theory, and single-point energies from CCSD(T)-F12b/cc-pVTZ-F12 theory, plus a term to correct approximately for electron correlation through CCSDT(Q). Three connected transition states are involved and rate constants were obtained via Multistructural Improved Canonical Variational Transition State Theory with Small Curvature Tunneling. Combination of experiment and theory leads to a recommended rate coefficient for hydrogen abstraction of k 1 = 6.3 × 10 –23 T 3.44 exp(+289 K/T) cm 3 molecule –1 s –1 . The minor channel for H + N 2 H 4 forming NH 2 + NH 3 was characterized computationally as well, to yield 5.0 × 10 –19 T 2.07 exp(-4032 K/T) cm 3 molecule –1 s –1 . Finally, these results are compared to several discordant prior estimates, and are employed in an overall mechanism to compare with measurements of half-lives of hydrazine in a shock tube.
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Multiple N–H and C–H Hydrogen Atom Abstractions Through Coordination-Induced Bond Weakening at Fe-Amine Complexes
We report the use of the reported Fe-phthalocyanine complex, PcFe (1; Pc = 1,4,8,11,15,18,22,25-octaethoxy-phthalocyanine), to generate PcFe–amine complexes 1-(NH 3 ) 2 , 1-(MeNH 2 ) 2 , and 1-(Me 2 NH) 2 . Treatment of 1 or 1-(NH 3 ) 2 to an excess of the stable aryloxide radical, 2,4,6-tritert-butylphenoxyl radical ( t Bu ArO•), under NH 3 resulted in catalytic H atom abstraction (HAA) and C–N coupling to generate the product 4-amino-2,4,6-tritert-butylcyclohexa-2,5-dien-1-one (2) and t Bu ArOH. Exposing 1-(NH 3 ) 2 to an excess of the trityl (CPh 3 ) variant, 2,6-di-tert-butyl-4-tritylphenoxyl radical ( Tr ArO • ), under NH 3 did not lead to catalytic ammonia oxidation as previously reported in a related Ru-porphyrin complex. However, pronounced coordination-induced bond weakening of both α N–H and β C–H in the alkylamine congeners, 1-(MeNH 2 ) 2 and 1-(Me 2 NH) 2 , led to multiple HAA events yielding the unsaturated cyanide complex, 1-(MeNH 2 )(CN), and imine complex, 1-(MeN=CH 2 ) 2 , respectively. Subsequent C–N bond formation was also observed in the latter upon addition of a coordinating ligand. Detailed computational studies support an alternating mechanism involving sequential N–H and C–H HAA to generate these unsaturated products.
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Proton, Electron, and Hydrogen-Atom Transfer Thermodynamics of the Metal–Organic Framework, Ti-MIL-125, Are Intrinsically Correlated to the Structural Disorder
Interfacial charge transfer reactions involving protons and/or electrons are fundamental to heterogeneous catalysis and many other reactions relevant to energy, chemical, and biological sectors. Metal–organic frameworks (MOFs) with redox-active metal-oxo nodes have emerged as candidate materials to examine these reactions with near-atomic-level precision, given their crystalline nature. Here, we employed a colloidally stable, Ti-based MOF, Ti-MIL-125, with different crystal sizes to examine catalytically relevant charge transfer thermodynamics. The Ti 8 (μ 2 -O) 8 (μ 2 -OH) 4 nodes structurally mimic TiO 2 , which has shown some PCET reactivity toward reactions of H 2 , O 2 , and others. In this report, we have demonstrated that a change in crystal size induces different amounts of structural disorder to the Ti-oxo node, further changing the thermodynamics of proton/electron/hydrogen-atom transfer reactions. Using electrochemical open-circuit potential (E OCP ) measurements, we have determined that all crystallites undergo a 1H + /1e – redox reaction, which, given the stoichiometry, can be considered as a net H atom transfer (HAT) reaction. The thermodynamics of this HAT reaction, the Ti 3+ O–H bond dissociation free energy (BDFE), was dependent on the crystal size of the MOF, as the decrease in crystal size induced more structural disorder. Our computational calculations have indicated that this difference in BDFE is due to a local change in the geometry of Ti cations, rather than the commonly invoked defects, such as the “missing-linker” defect sites. Individual proton/electron transfer (PT/ET) thermodynamics were also highly dependent on the crystal sizes. These were probed using pK a or band gaps (E g ), respectively. These findings suggest that, particularly when MOFs are nanosized with a large amount of structural disorder, they should no longer be considered “true” single-site catalysts; this is an implicit, but widespread assumption within the MOF-based catalysis field. Implications of these findings will be contrasted with structurally similar metal oxides like TiO 2 and other redox-active MOFs.
Bond dissociation free energy↗
Unconventional gas-phase preparation of the prototype polycyclic aromatic hydrocarbon naphthalene (C 10 H 8 ) via the reaction of benzyl (C 7 H 7 ) and propargyl (C 3 H 3 ) radicals coupled with hydrogen-atom assisted isomerization
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the interstellar medium and in meteorites such as Murchison and Allende and signify the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles (soot particles, interstellar grains). However, the predicted lifetime of interstellar PAHs of some 108 years imply that PAHs should not exist in extraterrestrial environments suggesting that key mechanisms of their formation are elusive. Exploiting a microchemical reactor and coupling these data with computational fluid dynamics (CFD) simulations and kinetic modeling, we reveal through an isomer selective product detection that the reaction of the resonantly stabilized benzyl (C 7 H 7 ) and the propargyl (C 3 H 3 ) synthesizes the simplest representative of PAHs – the 10π Hückel aromatic naphthalene (C 10 H 8 ) molecule – via the novel Propargyl Addition–BenzAnnulation (PABA) mechanism. The gas-phase preparation of naphthalene affords a versatile concept of the reaction of combustion and astronomically abundant propargyl radicals with aromatic radicals carrying the radical center at the methylene moiety (aromatic-CH 2 ) as a previously passed over source of aromatics in high temperature environments thus bringing us closer to an understanding of the aromatic universe we live in.
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Damped Ly α absorbers and atomic hydrogen in galaxies: the view of the GAEA model
ABSTRACT Using the GAEA semi-analytic model, we analyse the connection between Damped Ly α systems (DLAs) and H i in galaxies. Our state-of-the-art semi-analytic model is tuned to reproduce the local galaxy H i mass function, and that also reproduces other important galaxy properties, including the galaxy mass–gas metallicity relation. To produce catalogues of simulated DLAs we throw 105 random lines of sight in a composite simulated volume: dark matter haloes with log$(\frac{M_{200}}{ {\rm M}_{\odot }}) \ge 11.5$ are extracted from the Millennium Simulation, while for $9.2 \le \log (\frac{M_{200}}{ \mathrm{M}_{\odot }})\lt 11.5$ we use the Millennium II, and for $8 \le \log (\frac{M_{200}}{\mathrm{M}_{\odot }}) \lt 9.2$ a halo occupation distribution model. At 2 < z < 3, where observational data are more accurate, our fiducial model predicts the correct shape of the column density distribution function, but its normalization falls short of the observations, with the discrepancy increasing at higher redshift. The agreement with observations is significantly improved increasing both the H i masses and the disc radii of model galaxies by a factor of 2, as implemented ‘a posteriori’ in our 2M−2R model. In the redshift range of interest, haloes with $M_{200} \ge {10}^{11} \, \mathrm{M}_{\odot }$ give the major contribution to ΩDLA, and the typical DLA host halo mass is $\sim \!{10}^{11} \, \mathrm{M}_{\odot }$. The simulated DLA metallicity distribution is in relatively good agreement with observations, but our model predicts an excess of DLAs at low metallicities. Our results suggest possible improvements for the adopted modelling of the filtering mass and metal ejection in low-mass haloes.
Di Gioia, Serafina↗
Feasibility study for precisely measuring the EIC He 3 beam polarization with the Polarized Atomic Hydrogen Gas Jet Target polarimeter at RHIC
Not Available
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Breakup corrections to spin asymmetries in the He 3 beam polarization measurements with the Polarized Atomic Hydrogen Gas Jet Target
Not Available
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Replication Data for: Facilitating hydrogen atom migration via a dense phase on palladium islands to a surrounding silver surface
The data underlying this published work have been made publicly available in this repository as part of the IMASC Data Management Plan. This work was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0012573.
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Replication Data for: Facilitating hydrogen atom migration via a dense phase on palladium islands to a surrounding silver surface
The data underlying this published work have been made publicly available in this repository as part of the IMASC Data Management Plan. This work was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0012573.
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