The transition state for beta-hydride elimination in alkyl groups on the Pt(111) surface has been probed by studying the effects of fluorine substitution on the barriers to beta-hydride elimination, DeltaE++(betaH). Four different fluoroalkyl groups have been formed on the Pt(111) surface by dissociative adsorption of four fluoroalkyl iodides: RCH(2)CH(2)-I (R = CF(3), CF(3)CH(2), and CF(3)CF(2...

The FeMoco of nitrogenase is an iron-sulfur cluster with exceptional bond-reducing abilities. ENDOR studies have suggested that E4, the state that binds and reduces N2, contains bridging hydrides as part of the active-site iron-sulfide cluster. However, there are no examples of any isolable iron-sulfide cluster with a hydride, which would test the feasibility of such a species. Here, we describ...

The insertion, elimination and isomerisation of octenes with di-n-octylaluminium hydride [HAl(Oct)2], tri-n-octylaluminium [Al(Oct)3] and sec-octylaluminium species have been studied as individual steps in a putative aluminium based contrathermodynamic olefin isomerisation process. While elimination of 1-octene from [Al(Oct)3] is energetically unfavourable, the process is driven by high tempera...

An electrochemical hydride generation (ECHG) technique was developed to improve the determination of thallium by atomic spectrometry. The technique is based on the catholyte variation system for production of thallium hydride. Using Pb-Sn alloy as cathode, a transient peak shaped signal was achieved and its height, the maximum absorbance value, was taken as an analytical parameter. Parameters t...

A comprehensive analysis of the network of coupled motions correlated to hydride transfer in dihydrofolate reductase is presented. Hybrid quantum/classical molecular dynamics simulations are combined with a rank correlation analysis method to extract thermally averaged properties that vary along the collective reaction coordinate according to a prescribed target model. Coupled motions correlate...

The reaction betw een catalytically prepared m agnesium hydride (M gH 2*) and [TiCl3(T H F )3] in a molar ratio o f 1.5:1 in T H F yields a highly pyrophoric, X-ray am orphous titanium hydride precipitate with the com position [TiH2 -(M gC l2 -2 T H F )0.2-o.3] (2). This novel titanium hydride has been characterized through hydrolysis and iodolysis, as well as through therm olysis to Ti* and H ...

High-pressure metal hydride vehicular hydrogen storage systems can offer good overall gravimetric and volumetric hydrogen densities. Enhanced heat transfer techniques will be essential to achieve established goals for tank filling times. A numerical model is developed to simulate the hydrogen filling process of a subscale high-pressure metal hydride (Ti1.1CrMn) system. The model is validated by...

Novel inorganic alkali and alkaline earth hydrides of the f o r m u l a MH *, MH 2 * , and MH X * wherein M is the metal, X , is a halide, and H * comprises a novel high binding energy hydride ion were synthesized in a high temperature gas cell by reaction of atomic hydrogen with a catalyst and MH , MH 2 , or MX corresponding to an alkali metal or alkaline e a r t h metal compound, respectively...

Frustrated Lewis pair (FLP) chemistry enables a rare example of alkyne 1,2-hydrocarbation with N-methylacridinium salts as the carbon Lewis acid. This 1,2-hydrocarbation process does not proceed through a concerted mechanism as in alkyne syn-hydroboration, or through an intramolecular 1,3-hydride migration as operates in the only other reported alkyne 1,2-hydrocarbation reaction. Instead, in th...