Brønsted acid HNTf2 (Tf = SO2CF3) mediated dehydrogenative hydride abstraction from (L(1))BH3 () and (L(2))BH3 () (L(1) = IPrCH2 = 1,3-(2,6-di-isopropylphenyl)imidazol-2-methylidene (); L(2) = SIPrCH2 = 1,3-(2,6-di-isopropylphenyl)imidazolidin-2-methylidiene ()) affords thermally stable hydride bridged mono-cationic hydrido boron compounds [{(L(1))BH2}2(μ-H)](NTf2) () and [{(L(2))BH2}2(μ-H)](NT...

A study of an enzyme that reacts with the sulfenic acid produced by the alliinase in Petiveria alliacea L. (Phytolaccaceae) to yield the P. alliacea lachrymator (phenylmethanethial S-oxide) showed the protein to be a dehydrogenase. It functions by abstracting hydride from sulfenic acids of appropriate structure to form their corresponding sulfines. Successful hydride abstraction is dependent up...

We use quantized molecular dynamics simulations to characterize the role of enzyme vibrations in facilitating dihydrofolate reductase hydride transfer. By sampling the full ensemble of reactive trajectories, we are able to quantify and distinguish between statistical and dynamical correlations in the enzyme motion. We demonstrate the existence of nonequilibrium dynamical coupling between protei...

The group's recent advances in catalytic carbon-to-heteroatom bond forming reactions of alkenes and alkynes are described. For the C-O bond formation reaction, a well-defined bifunctional ruthenium-amido catalyst has been successfully employed for the conjugate addition of alcohols to acrylic compounds. The ruthenium-hydride complex (PCy(3))(2)(CO)RuHCl was found to be a highly effective cataly...

Salt metathesis reactions of Cp(2)(NR(2))ZrX (X = Cl, I, OTf) and lithium hydrosilazides ultimately afford hydride products Cp(2)(NR(2))ZrH that suggest unusual β-hydrogen elimination processes. A likely intermediate in one of these reactions, Cp(2)Zr[N(SiHMe(2))t-Bu][N(SiHMe(2))(2)], is isolated under controlled synthetic conditions. Addition of alkali metal salts to this zirconium hydrosilazi...

The homolytic bond dissociation energy of the titanium neutral hydride D ‘(Ti-H) is determined experimentally for the first time by using guided ion beam tandem mass spectrometry to measure the kinetic energy dependence of the endothermic hydride abstraction reactions of Ti+ with methylamine, dimethylamine, and trimethylamine. From the thresholds of these reactions, the value of D ‘(Ti-H) = 2.1...

Understanding the corrosion of uranium is important for its safe, long-term storage. Uranium metal corrodes rapidly in air, but the exact mechanism remains subject to debate. Atom Probe Tomography was used to investigate the surface microstructure of metallic depleted uranium specimens following polishing and exposure to moist air. A complex, corrugated metal-oxide interface was observed, with ...

CePtAl absorbs hydrogen up to a concentration of 1.1(1)H mol−1 at room temperature. The formation of this hydride CePtAlH1.1 that loses hydrogen in air corresponds to a plateau pressure of 0.08–0.1 MPa. Its absorption–desorption is practically reversible which can present a potential interest for applications (but only a few due to the high price of the material) around room temperature and nor...

Working as an extension of a newly developed method for a capillary electrophoretic analysis of purine nucleotides, nucleosides, bases, and catabolism, an assay of the differential metabolic properties by a novel organosiliceous anionic hydride compound, silica hydride, was evaluated with Chinese hamster ovary mitochondria using a 50-microm poly(acryloylaminopropanol)-coated, fused-silica capil...

We have synthesized a new metastable metal hydride with promising hydrogen storage properties. Body centered cubic (bcc) magnesium niobium hydride (Mg(0.75)Nb(0.25))H(2) possesses 4.5 wt% hydrogen gravimetric density, with 4 wt% being reversible. Volumetric hydrogen absorption measurements yield an enthalpy of hydride formation of -53 kJ mol(-1) H(2), which indicates a significant thermodynamic...