Source Of Hydrogen Atoms Research Articles

Thermodynamics of various F420 coenzyme models as sources of electrons, hydride ions, hydrogen atoms and protons in acetonitrile.

32 F420 coenzyme models with alkylation of the three different N atoms (N1, N3 and N10) in the core structure (XFH(-)) were designed and synthesized and the thermodynamic driving forces (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the 32 XFH(-) releasing hydride ions, hydrogen atoms and electrons, the thermodynamic driving forces of the 32 XFH˙ releasing protons and hydrogen atoms and the thermodynamic driving forces of XF(-)˙ releasing electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The effects of the methyl group at N1, N3 and N10 and a negative charge on N1 and N10 atoms on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were examined; the results show that seating arrangements of the methyl group and the negative charge have remarkably different effects on the thermodynamic properties of the F420 coenzyme models and their related reaction intermediates. The effects of the substituents at C7 and C8 on the six thermodynamic driving forces of the F420 coenzyme models and their related reaction intermediates were also examined; the results show that the substituents at C7 and C8 have good Hammett linear free energy relationships with the six thermodynamic parameters. Meanwhile, a reasonable determination of possible reactions between members of the F420 family and NADH family in vivo was given according to a thermodynamic analysis platform constructed using the elementary step thermodynamic parameter of F420 coenzyme model 2FH(-) and NADH model MNAH releasing hydride ions in acetonitrile. The information disclosed in this work can not only fill a gap in the chemical thermodynamics of F420 coenzyme models as a class of very important organic sources of electrons, hydride ions, hydrogen atoms and protons, but also strongly promote the fast development of the chemistry and applications of F420 coenzyme.

Hydrotrifluoromethylation and iodotrifluoromethylation of alkenes and alkynes using an inorganic electride as a radical generator.

The trifluoromethyl (CF3) group is a staple synthon that can alter the physical and chemical properties of organic molecules. Despite recent advances in trifluoromethylation methods, the development of a general synthetic methodology for efficient and selective trifluoromethylation remains an ongoing challenge motivated by a steadily increasing demand from the pharmaceutical, agrochemical and materials science industries. In this article, we describe a simple, efficient and environmentally benign strategy for the hydrotrifluoromethylation of unactivated alkenes and alkynes through a radical-mediated reaction using an inorganic electride, [Ca2N](+) · e(-), as the electron source. In the transformation, anionic electrons are transferred from [Ca2N](+) · e(-) electrides to the trifluoromethylating reagent CF3I to initiate radical-mediated trifluoromethylation. The role of ethanol is pivotal in the transformation, acting as the solvent, an electron-releasing promoter and a hydrogen atom source. In addition, iodotrifluoromethylation of alkynes proceeds selectively upon the control of electride amount.

Photofragmentation spectra of halogenated methanes in the VUV photon energy range.

In this paper an investigation of the photofragmentation of dihalomethanes CH2X2 (X = F, Cl, Br, I) and chlorinated methanes (CH(n)Cl(4-n) with n = 0-3) with VUV helium, neon, and argon discharge lamps is reported and the role played by the different halogen atoms is discussed. Halogenated methanes are a class of molecules used in several fields of chemistry and the study of their physical and chemical proprieties is of fundamental interest. In particular their photodissociation and photoionization are of great importance since the decomposition of these compounds in the atmosphere strongly affects the environment. The results of the present work show that the halogen-loss is the predominant fragmentation channel for these molecules in the VUV photon energy range and confirm their role as reservoir of chlorine, bromine, and iodine atoms in the atmosphere. Moreover, the results highlight the peculiar feature of CH2F2 as a source of both fluorine and hydrogen atoms and the characteristic formation of I2(+) and CH2(+) ions from the photofragmentation of the CH2I2 molecule.

Electroplating of Rhodium/Si(111) Junctions for Solar Fuel Generation: Effects of Hydrogen Diffusion

Surface chemical and electronic properties of electroplated Rh/Si(111)-interfaces were investigated by cyclovoltammetry, HRTEM, electrochemical impedance and synchrotron radiation photoelectron spectroscopy (SRPES). The strong adsorption of hydrogen onto (photo)-electrochemical deposited Rh crystallites brings about a source of atomic hydrogen, which diffuses into the silicon substrate. The incorporation of hydrogen turns the underlying substrate amorphous and passivates dopant energy states. This inverts the conduction type of the semiconductor with the formation of an apparent surface pn-junction which controls the electronic behavior of the metal/semiconductor contact.

Suprathermal oxygen and hydrogen atoms in the upper Martian atmosphere

The processes of kinetics and transport of hot oxygen and hydrogen atoms in the transition (from the thermosphere to the exosphere) region of the upper Martian atmosphere are studied. The reaction of dissociative recombination of the principal ionospheric ion O2+ with thermal electrons in the ionosphere of Mars served as the source of hot oxygen atoms. The process of momentum and energy transfer in elastic collisions between hot oxygen atoms and atmospheric hydrogen atoms with thermal energies was regarded as the source of hot hydrogen atoms. The kinetic energy distribution functions are determined for suprathermal oxygen and hydrogen atoms. It is shown that the exosphere is populated with a significant number of suprathermal oxygen atoms with kinetic energies ranging up to the escape energy of 2 eV (i.e., the hot oxygen Martian corona is formed). The transfer of energy from hot oxygen atoms to thermal hydrogen atoms creates an additional nonthermal flux of atomic hydrogen escaping from the Martian atmosphere.

(Invited) A Novel Approach to Clean Surface for High Mobility Channel Materials with In Situ Atomic Hydrogen Clean

A number of non-silicon channel materials have been considered for advanced CMOS devices such as SiGe, Ge and GeSn (PMOS) as well as various III-V materials combinations including InGaAs and GaAs (NMOS). Surfaces cleaning process is critical to make a better interface contact in devices. This study demonstrates a method of surface cleaning on Ge/III-V channel using thermal atomic hydrogen source. This technique has several advantages over conventional wet, thermal, or plasma cleaning such as lower temperatures, no surface damage, less impurities, selective removal, and large area scalability. This will be a good candidate technology for the future non-Si CMOS technology beyond 10 nm node with scalability to 450 mm wafer size.

A Synthetic and Mechanistic Investigation of the Chromium Tricarbonyl-Mediated Masamune–Bergman Cyclization. Direct Observation of a Ground-State Triplet p-Benzyne Biradical

A new room-temperature chromium tricarbonyl- mediated cycloaromatization of enediynes is reported. The reaction occurs with both cyclic and acyclic enediynes in the presence of (Cr(CO)3(η 6 -naphthalene)) and both a coordinating solvent and a hydrogen atom source, providing chromiumarene complexes in reasonable yield and good diastereocontrol. The mechanism of the reaction has been probed through DFT computational and spectroscopic methods. These studies suggest that direct C1�C6 bond formation from an η 6 -enediyne complex is the lowest- energy path, forming a metal-bound p-benzyne biradical. NMR spectroscopy suggests that enediyne alkene coordination occurs in preference to alkyne coordination, forming a THF-stabilized olefin intermediate; subsequent alkyne coordination leads to cyclization. While biradical quenching occurs rapidly and primarily via the singlet biradical, the triplet state biradical is detectable by EPR spectroscopy, suggesting intersystem crossing to a triplet ground state.

Quantification of the atomic hydrogen flux as a function of filament temperature and H2 flow rate

An isothermal sensor is developed to quantify the atomic hydrogen flux on a surface, which can be located at any distance from the molecular hydrogen cracking unit. This flux is determined from the measured heat effect due to recombination of atomic hydrogen at the sensor surface. The temperature of the sensor was kept constant at 350°C to keep the heat losses constant during the measurement. Other heat flows due to radiative, conductive, and convective phenomena were quantified with targeted measurements. The design of the sensor allows ample area for the atomic hydrogen recombination reaction; thus enabling the flux values to be determined with high accuracy (errors were between ±8.3×1015 and ±3.3×1016atcm-2s-1). The atomic hydrogen flux, generated with a commercial atomic hydrogen source was measured as a function of the filament temperature in the range of 1400-1950°C and H2 gas flow in the range of 7.44×10-6 to 7.44×10-5mol/s (10–100 sccm). These measurements showed that the atomic hydrogen flux increases with both filament temperature and H2 flux.

Selective Homogeneous and Heterogeneous Catalytic Conversion of Methanol/Dimethyl Ether to Triptane

The demand for specific fuels and chemical feed-stocks fluctuates, and as a result, logistical mismatches can occur in the supply of their precursor raw materials such as coal, biomass, crude oil, and methane. To overcome these challenges, industry requires a versatile and robust suite of conversion technologies, many of which are mediated by synthesis gas (CO + H(2)) or methanol/dimethyl ether (DME) intermediates. One such transformation, the conversion of methanol/DME to triptane (2,2,3-trimethylbutane) has spurred particular research interest. Practically, triptane is a high-octane, high-value fuel component, but this transformation also raises fundamental questions: how can such a complex molecule be generated from such a simple precursor with high selectivity? In this Account, we present studies of this reaction carried out in two modes: homogeneously with soluble metal halide catalysts and heterogeneously over solid microporous acid catalysts. Despite their very different compositions, reaction conditions, provenance, and historical scientific context, both processes lead to remarkably similar products and mechanistic interpretations. In both cases, hydrocarbon chains grow by successive methylation in a carbocation-based mechanism. The relative rates of competitive processes-chain growth by methylation, chain termination by hydrogen transfer, isomerization, and cracking-systematically depend upon the structure of the various hydrocarbons produced, strongly favoring the formation of the maximally branched C(7) alkane, triptane. The two catalysts also show parallels in their dependence on acid strength. Stronger acids exhibit higher methanol/DME conversion but also tend to favor chain termination, isomerization, and cracking relative to chain growth, decreasing the preference for triptane. Hence, in both modes, there will be an optimal range: if the acid strength is too low, activity will be poor, but if it is too high, selectivity will be poor. A related reaction, the methylative homologation of alkanes, offers the possibility of upgrading low-value refinery byproducts such as isobutane and isopentane to more valuable gasoline components. With the addition of adamantane, a hydride transfer catalyst that promotes activation of alkanes, both systems effectively catalyze the reaction of methanol/DME with lighter alkanes to produce heavier ones. This transformation has the further advantage of providing stoichiometric balance, whereas the stoichiometry for conversion of methanol/DME to alkanes is deficient in hydrogen and requires rejection of excess carbon in the form of carbon-rich arenes, which lowers the overall yield of desired products. Alternatively, other molecules can serve as sacrificial sources of hydrogen atoms: H(2) on heterogeneous catalysts modified by cations that activate it, and H(3)PO(2) or H(3)PO(3) on homogeneous catalysts. We have interpreted most of the features of these potentially useful reactions at a highly detailed level of mechanistic understanding, and we show that this interpretation applies equally to these two widely disparate types of catalysts. Such approaches can play a key role in developing and optimizing the catalysts that are needed to solve our energy problems.

Synthesis and structure of the first clathrochelate iron(ii) tris-dioximates with inherent nitrile substituent(s) and new dehalogenation – reduction reaction at a quasi-aromatic macrobicyclic framework

Monoribbed-substituted mono- and dicyano-functionalized iron(II) macrobicycles were obtained for the first time by the reaction of iron(II) diiodoclathrochelate precursor with copper(I) cyanide-triphenylphosphine complex under mild conditions. The target dinitrile clathrochelate is a minor product of this reaction, whereas the major product contains only one cyano group. The clathrochelates obtained were characterized using elemental analysis, (1)H and (13)C{(1)H} NMR, IR and UV-vis spectroscopy, MALDI-TOF spectrometry and X-ray diffraction crystallography. The geometry of their FeN(6)-coordination polyhedra is intermediate between a trigonal prism (TP) and a trigonal antiprism (TAP); the distortion angles, φ, are 22.6-24.7°. In the molecule of the precursor, the Fe-N distances are close, whereas in the mononitrile macrobicycles those for their functionalized chelate fragments are substantially smaller than the corresponding distances in the α-benzyldioximate moieties. The heights, h, of the TP-TAP coordination polyhedra and the average bite angles, α, (2.33 Å and 39°, respectively) are the same for the X-rayed clathrochelates. The UV-vis spectra indicate a dramatic redistribution of the electron density in the π-conjugated clathrochelate framework caused by functionalization with inherent nitrile substituents. The proposed mechanism of the dehalogenation-reduction reaction of iron(II) diiodoclathrochelate resulting in substitution of their iodine atoms by a cyano group and hydrogen atom includes the anion-radical hydrodehalogenation of this precursor with acetonitrile as a source of hydrogen atom. Then, the monomethinemonoiodine macrobicyclic product underwent a substitution with a cyano group only. The copper(I) cyanide-triphenylphosphine-acetonitrile system is proposed as a tool for the synthesis of nitrile derivatives of electron-withdrawing heterocycles starting from their halogen-containing precursors.

Simple Low-Outgassing Atomic Hydrogen Source

Simple Low-Outgassing Atomic Hydrogen Source

What Are the Differences between Ascorbic Acid and NADH as Hydride and Electron Sources in Vivo on Thermodynamics, Kinetics, and Mechanism?

Ascorbic acid (AscH(2)) and dihydronicotinamide adenine dinucleotide (NADH) are two very important natural redox cofactors, which can be used as hydride, electron, and hydrogen atom sources to take part in many important bioreduction processes in vivo. The differences of the two natural reducing agents as hydride, hydrogen atom, and electron donors in thermodynamics, kinetics, and mechanisms were examined by using 5,6-isopropylidene ascorbate (iAscH(-)) and β-D-glucopyranosyl-1,4-dihydronicotinamide acetate (GluNAH) as their models, respectively. The results show that the hydride-donating ability of iAscH(-) is smaller than that of GluNAH by 6.0 kcal/mol, but the electron-donating ability and hydrogen-donating ability of iAscH(-) are larger than those of GluNAH by 20.8 and 8.4 kcal/mol, respectively, which indicates that iAscH(-) is a good electron donor and a good hydrogen atom donor, but GluNAH is a good hydride donor. The kinetic intrinsic barrier energy of iAscH(-) to release hydride anion in acetonitrile is larger than that of GluNAH to release hydride anion in acetonitrile by 6.9 kcal/mol. The mechanisms of hydride transfer from iAscH(-) and GluNAH to phenylxanthium perchlorate (PhXn(+)), a well-known hydride acceptor, were examined, and the results show that hydride transfer from GluNAH adopted a one-step mechanism, but the hydride transfer from iAscH(-) adopted a two-step mechanism (e-H(•)). The thermodynamic relation charts (TRC) of the iAscH(-) family (including iAscH(-), iAscH(•), iAsc(•-), and iAsc) and of the GluNAH family (including GluNAH, GluNAH(•+), GluNA(•), and GluNA(+)) in acetonitrile were constructed as Molecule ID Cards of iAscH(-) and of GluNAH in acetonitrile. By using the Molecule ID Cards of iAscH(-) and GluNAH, the character chemical properties not only of iAscH(-) and GluNAH but also of the various reaction intermediates of iAscH(-) and GluNAH all have been quantitatively diagnosed and compared. It is clear that these comparisons of the thermodynamics, kinetics, and mechanisms between iAscH(-) and GluNAH as hydride and electron donors in acetonitrile should be quite important and valuable to diagnose and understand the different roles and functions of ascorbic acid and NADH as hydride, hydrogen atom, and electron sources in vivo.

Pyrolysis of Ethyl Iodide as Hydrogen Atom Source: Kinetics and Mechanism in the Temperature Range 950–1200 K

Abstract Ethyl iodide is a well known H atom precursor in shock tube experiments. In the present work, we study peculiarities, when C2H5I is used under conditions, where its decomposition is not longer fast compared to consecutive bimolecular reactions. On the basis of shock tube experiments with detection of H and I atoms by resonance absorption spectrometry, accompanied by quantum chemical (CCSD(T)/6-311G//CCSD/6-311G) and statistical rate theory calculations, we propose a small mechanism (5 reactions, 7 species) and kinetic data, which allow an adequate description of C2H5I pyrolysis as a H atom source down to temperatures between 950 and 1200 K at pressures ranging from 1 to 4 bar: C2H5I→C2H5 + I (1), k 1 = 9.9 × 1012 exp(−23200 K/T) s−1; C2H5 + M→C 2H4 + H + M (2), k 2 = 1.7 × 10−6 exp(−16800 KT) cm3 s−1 [D. L. Baulch et al., J. Phys. Chem. Ref. Data 34 (2005) 757]; C2H5I→C2H4 + HI (3), k 3 = 1.7 × 1013 exp(−26680 KT) s−1; H + HI→H2 + I (4), k 4 = 7.9 × 10−11 exp(−330 KT) cm3 s−1 [D. L. Baulch et al., J. Phys. Chem. Ref. Data 10(Suppl. 1) (1981) 1]; C2H5I + H→C2H5 + HI (5), k 5 = 7.0 × 10−9 exp(−3940 KT) cm3 s−1. The latter bimolecular abstraction step turned out crucial for an adaquate d escription of the hydrogen atom concentration-time profiles in the above mentioned temperature and pressure range for initial concentrations [C2H5I]0 > 2 × 1013 cm−3 corresponding to mole fractions > 1 ppm.

ChemInform Abstract: Reducing the Cost, Smell, and Toxicity of the Barton Reductive Decarboxylation: Chloroform as the Hydrogen Atom Source.

AbstractThe use of chloroform as a solvent is crucial as it serves also as a hydrogen source.

FTIR Matrix-Isolation Study of the Reaction Products of Vanadium Atoms with Propene: Observation of Allylvanadium Hydride As a Precursor to Sacrificial Hydrogenation of Propene

Vanadium atoms have been reacted with different partial pressures of propene in Ar under matrix-isolation conditions, and the products have been observed using Fourier transform infrared (FTIR) spectroscopy. Under dilute propene in Ar conditions, new features are observed in the IR spectra corresponding to a C-H insertion product, identified here as H-V-(η(3)-allyl). Use of d(3)-propene (CD(3)-CH═CH(2)) demonstrates that the initial V-atom insertion occurs at the methyl group of the propene molecule, and DFT calculations have been used to support the identity of the initial product. Upon increasing the partial pressure of propene, additional features corresponding to propane (C(3)H(8)) are observed, with the hydrogen-atom source for the observed hydrogenation demonstrated to be additional propene units. Analysis of a systematic increase in the partial pressure of propene in the system demonstrates that the yield of propane correlates with the decrease of the allyl product, demonstrating the H-V(allyl) species as a reactive intermediate in the overall hydrogenation process. An overall mechanism is proposed to rationalize the formation of the insertion product and ultimately the products of hydrogenation, which agrees with previous gas-phase and matrix-isolation work involving propene and the related system, ethene.

Characterization of a neutral atomic hydrogen source developed in the perspective of carbon materials etching study

This paper deals with the characterization of an atomic hydrogen source created in a radio-frequency reactor with a helicon configuration. To achieve this purpose, optical (laser induced fluorescence) and electrical (Langmuir probe) diagnostics are used to monitor the behavior of the species composing the plasma. The influence of pressure, gas composition, and impact of the magnetic fields (in the source and diffusion chambers) are investigated.

Reducing the Cost, Smell, and Toxicity of the Barton Reductive Decarboxylation: Chloroform as the Hydrogen Atom Source

When used as solvent, chloroform was found to act as a hydrogen atom donor in Barton reductive decarboxylation reactions. Chloroform offers a substantial practical advantage over pre-existing hydrogen atom donors.

Radical Chain Reduction of Alkylboron Compounds with Catechols

The conversion of alkylboranes to the corresponding alkanes is classically per-formed via protonolysis of alkylboranes. This simple reaction requires the use of severe reaction conditions, that is, treatment with a carboxylic acid at high temperature (>150 °C). We report here a mild radical procedure for the transformation of organoboranes to alkanes. 4-tert-Butylcatechol, a well-established radical inhibitor and antioxidant, is acting as a source of hydrogen atoms. An efficient chain reaction is observed due to the exceptional reactivity of phenoxyl radicals toward alkylboranes. The reaction has been applied to a wide range of organoboron derivatives such as B-alkylcatecholboranes, trialkylboranes, pinacolboronates, and alkylboronic acids. Furthermore, the so far elusive rate constants for the hydrogen transfer between secondary alkyl radical and catechol derivatives have been experimentally determined. Interestingly, they are less than 1 order of magnitude slower than that of tin hydride at 80 °C, making catechols particularly attractive for a wide range of transformations involving C-C bond formation.

Recombination of hydrogen atoms on fine-grain graphite

The probability of recombination of hydrogen atoms on surfaces of fine-grain graphite EK98 was investigated as a function of surface roughness. The source of hydrogen atoms used in this experiment was weakly ionised plasma created with an inductively coupled radiofrequency generator at pressures from 30Pa to 175Pa in hydrogen. Hydrogen atom density was measured by means of fibre optic catalytic probes. The recombination coefficient of the graphite samples was determined by observing their impact on the spatial distribution of the atom density in a closed side-arm of the reactor. Smith's diffusion model was used to calculate the values of the recombination coefficient. The measured recombination coefficient was found to increase much faster than the measured effective surface. This discrepancy is explained by the fact that on a surface which is not perfectly flat, there is a finite probability for multiple collisions. Impinging atoms collide more than once with the surface before they are reflected into the surface, which results in a larger probability of recombination.

Surface reactivity ofV2O5(001): Effects of vacancies, protonation, hydroxylation, and chlorination

Using density-functional theory we analyze the thermodynamic stability of partially reduced, protonated, hydroxylated, and chlorinated ${\mathrm{V}}_{2}$O${}_{5}$(001) surfaces under flue gas conditions. These surfaces are characterized geometrically through surface relaxation calculations and electronically through charge distribution and density-of-states analysis to understand the change in surface reactivity under different pressure and temperature conditions, with a primary focus on coal-fired flue gas conditions. The stoichiometric surface is found to be the most favorable termination under flue gas conditions, but at low oxygen partial pressures (i.e., ultra-high-vacuum conditions) and elevated temperatures, the partially reduced ${\mathrm{V}}_{2}$O${}_{5}$(001) surfaces with one or two vanadyl oxygen vacancies are found to be stable. A surface semiconductor-to-metal transformation takes place with the addition of oxygen vacancies indicated by a decrease in the band gap. The protonation of the ${\mathrm{V}}_{2}$O${}_{5}$(001) surface only takes place at low oxygen partial pressures where the main source or sink of hydrogen atoms comes from ${\mathrm{H}}_{2}$. The study of the thermodynamic stability of protonated surfaces and surfaces with dissociated water with both H-- and OH-- groups indicated that these surfaces are not stable under flue gas conditions. Chlorinated surfaces were not stable under the flue gas and the coverage conditions tested. Larger HCl concentrations or smaller coverages may lead to stable chlorinated structures; however, the small coverages required to accurately represent the chlorine flue gas concentrations would require much larger unit-cell sizes that would be too computationally expensive. From this work it is evident that the stoichiometric surface of ${\mathrm{V}}_{2}$O${}_{5}$ is the most stable under flue gas conditions, and likely reactivity corresponding to NO${}_{x}$ reduction, surface chlorination, and mercury oxidation stems from support effects on the vanadia catalyst, which influences the vanadium oxidation state and subsequent surface reactivity.