Density functional theory calculations reveal a complete reaction mechanism with detailed energy profiles and transition state structures for the dehydrogenation of formic acid catalyzed by an iron complex, [P(CH2CH2PPh2)3FeH](+). In the cationic reaction pathway, a β-hydride elimination process is confirmed to be the rate-determining step in this catalytic reaction. A potential reaction pathwa...

A dinuclear Co complex with bis(pyridyl)pyrazolato (bpp(-)) and terpyridine (trpy) ligands, [Co(III)2(trpy)2(μ-bpp)(OH)(OH2)](4+) (1(4+)), undergoes three-electron reduction by cobaltocene in acetonitrile to produce 1(+), which is in the protonation equilibrium with the Co(II)Co(III)-hydride complex, and the further protonation of the hydride by trifluoroacetic acid yields hydrogen quantitative...

The excited-state hydride release from 10-methyl-9-phenyl-9,10-dihydroacridine (PhAcrH) was investigated using steady-state and time-resolved UV/vis absorption spectroscopy. Upon excitation, PhAcrH is oxidized to the corresponding iminium ion (PhAcr(+)), while the solvent (acetonitrile/water mixture) is reduced (52% of PhAcr(+) and 2.5% of hydrogen is formed). The hydride release occurs from th...

A conserved residue at the dihydrofolate binding site of dihydrofolate reductase (EC 1.5.1.3), leucine-54, was replaced with glycine to ascertain the role of this hydrophobic amino acid. The effect of the mutation is both to increase the dissociation rate of dihydrofolate and decrease the rate of hydride transfer thus changing the rate-limiting step in catalysis from product loss (leucine-54) t...

In this review article, the fundamentals of electrochemical reactions involving metal hydrides are explained, followed by a report of recent progress in hydrogen storage alloys for electrochemical applications. The status of various alloy systems, including AB₅, AB₂, A₂B₇-type, Ti-Ni-based, Mg-Ni-based, BCC, and Zr-Ni-based metal hydride alloys, for their most important electrochemical applicat...

We measured the reaction kinetics of electrochemical reduction CO2 to formate on Pd/C and evaluated several proposed mechanisms, by comparing model-described observed rates formation HCOO– H2 as a function parameters (pH2, pCO2, potential). An ?-/?-hydride mechanism, based an ?-hydride phase active for ?-hydride Pd-phase hydrogen evolution, described experimental data our other laboratories rep...

Hydrosilane-B(C6F5)3 adducts were found to activate zirconocene dihalides and generate ternary catalytic systems possessing moderate to high activity in ethylene polymerization to high density polyethylene (HDPE). The activation efficacy of the adducts increased with increasing hydride donor ability and decreased with steric crowding of the particular hydrosilane used. NMR investigation of the ...

In this paper, a mathematical model for the cycling electrochemical capacity of hydride electrodes was deduced on the basis of activation and degradation of hydride materials. A cycle life model was deduced on introducing the activation and degradation factors into the electrochemical polarization equation which included concentration polarization, phase transformation polarization and electroc...

The controlled out-diffusion method was employed to induce a nuclear reaction in a palladium (Pd) plate with a MnOx film. The time-resolved mass spectra for Pd deuteride revealed tritium (T) production during the outdiffusion experiment. Similar time behaviors of mass number 1-4 and 6 in the spectra was also observed for Pd hydride. Film blackening was observed for most Pd deuteride as well as ...

Hydride generation techniques are used routinely for the determination of As, Se, and Sb in environmental samples. Advantages include high sensitivity, simplicity and relative freedom from interferences. The current method for the hydride generation determination of As and Se, as outlined in the USEPA manual SW-846, utilizes zinc slurry methodology. A batch type method is described. Batch type ...