Hydride attack at a ferric heme-NO to give an Fe-HNO intermediate is a key step in the global N-cycle. We demonstrate differential reactivity when six- and five-coordinate ferric heme-NO models react with hydride. Although Fe-HNO formation is thermodynamically favored from this reaction, Fe-H formation is kinetically favored for the 5C case.

Ni-C in the O(2)-tolerant hydrogenase I from Aquifex aeolicus binds a hydride weaker than that in O(2)-sensitive hydrogenases. This is in line with the enhanced light-sensitivity of Ni-C, greater lability of the hydride complex and increased catalytic redox potentials relevant to bio-H(2) oxidation.

The use of hydride generation is often useful in environmental analysis. The normal acid sodium tetrahydroborate reaction provides exceptional sensitivity with continuous flow hydride generators. In some situations there are interferences which will mask the sensitivity. An alternative chemistry system is described here and is shown to offer similar sensitivity to that normally used. A commerci...

Aluminumoxyhydride (HAlO) has been obtained by the reaction of aluminum hydride with the siloxane (Me2HSi)2O or the stannoxane (Bu3Sn)2O as an amorphous colorless insoluble powder. The highest-purity product resulted from the reaction of H3Al.NMe3 with (Me2HSi)2O. However, HAlO suspensions in tetrahydrofuran (THF) of sufficient quality for synthetic applications can be prepared from commerciall...

Mutant forms of thymidylate synthase (TS) with substitutions at the conserved active site residue, Trp 80, are deficient in the hydride transfer step of the TS reaction. These mutants produce a beta-mercaptoethanol (beta-ME) adduct of the 2'-deoxyuridine-5'-monophosphate (dUMP) exocyclic methylene intermediate. Trp 80 has been proposed to assist hydride transfer by stabilizing a 5,6,7,8-tetrahy...

Hydride formation was studied on Pd particles supported on SiO2, and the results were evaluated with reference to a corresponding ZnO-promoted Pd/SiO2 catalyst reported recently. Pd particles (mean size, ~5 nm) were epitaxially grown on NaCl(001) cleavage faces and subsequently covered by a layer of amorphous SiO2, thereby maintaining their epitaxial orientation. The films were subjected to var...

A variant of the semipinacol rearrangement that was observed in our laboratory has been applied to the synthesis of several furanose and pyranose derivatives. The process consists of an "orchestrated" [1,2]-hydride shift with departure of a leaving group from the opposite face. Transient formation of a C=O group is followed by rapid transfer of a hydride-equivalent from the same face from which...

Radically different! The hydrosilylation of pyridines and quinolines is strictly 1,4-selective and likely involves an ionic one-step rather than the established radical two-step hydride transfer from a ruthenium(II) hydride complex onto the respective pyridinium and quinolinium ion intermediates (see scheme; Ar(F) =3,5-(CF3)2C6H3). Even 4-substituted substrates react highly regioselectively. Is...

The first elemental cluster with hexacapped trigonal bipyramidal geometry is revealed in the luminescent undecanuclear silver complex which is stabilized by nine dithiocarbamate ligands and has an interstitial hydride. The hydride position within the Ag(11) cage is confirmed by a DFT investigation.

Three dimensional heat and mass transfer in a metal-hydrogen reactor are numerically studied using the control-volume-based finite element method (CVFEM).The distributions of the temperature and the hydride density on the hydriding process is presented and discussed. The effects of dimensions reactor, imposed hydrogen pressure, inlet temperature and hydride thermal conductivity in the reaction ...