Recent experiments have established the generality of superabundant vacancies (SAV) formation in metal hydrides. Aiming to elucidate this intriguing phenomenon and to clarify previous interpretations, we employ density-functional theory to investigate atomic mechanisms of SAV formation in fcc hydrides of Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au. We have found that upon H insertion, vacancy formation ...

In aqueous solutions, as in organic solvents, rhodium hydrides display the chemistry of one of the three limiting forms, i.e. {Rh(I)+ H+}, {Rh(II)+ H.}, and {Rh(III)+ H-}. A number of intermediates and oxidation states have been generated and explored in kinetic and mechanistic studies. Monomeric macrocyclic rhodium(II) complexes, such as L(H2O)Rh2+ (L = L1 = [14]aneN4, or L2 = meso-Me6[14]aneN...

The synthesis, structural characterisation and the properties of the Zintl hydrides AeE2H2 and AeAlSiH (Ae = Ba, Ca, Sr; E = Al, Ga, In, Si, Zn) are reported. The first hydride in this class of compounds is SrAl2H2 which was discovered under an experiment by Gingl, who hydrogenated SrAl2 at various temperatures. (Gingl et al, Journal of Alloys and Compounds 306 (2000) 127-132). The intention wa...

The reaction of the bis(pentalene)dititanium complex Ti2(μ:η5,η5-Pn†)2 (Pn† = C8H4(1,4-SiiPr3)2) with the N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene results in intramolecular C-H activation of one of the iPr methyl groups of a Pn† ligand and formation of a "tucked-in" bridging hydride complex. The "tuck-in" process is reversed by the addition of hydrogen, which yields a dihydr...

Complex aluminum hydrides with high hydrogen capacity are among the most promising solid-state storage materials. The present study determines thermal stability, dissociation energy, and electronic structures of alkali metal hydrides, MAlH4 (M = Li, Na, K, Cs), using first-principles density functional theory calculations in an attempt to gain insight into dehydrogenation mechanism these hydrid...

Zinc powder in aqueous alkaline media was employed to perform reductive amination of aldehydes with primary amines. The corresponding secondary amines were obtained in good yields along with minor amounts of hydrodimerization byproducts. The protocol is a green alternative to the use of complex hydrides in chlorinated or highly flammable solvents.