화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.124, No.25, 7610-7613, 2002
Homoleptic tetrahydrometalate anions MH4- (M = Sc, Y, La). Matrix infrared spectra and DFT calculations
Laser-ablated Sc, Y, and La atoms react with molecular hydrogen upon condensation in excess argon, neon, and deuterium to produce the metal dihydride molecules and dihydrogen complexes MH2 and (H-2)MH2. The homoleptic tetrahydrometalate anions ScH4-, YH4-, and LaH4- are formed by electron capture and identified by isotopic substitution (D-2, HD, and H-2 + D-2 mixtures). Doping with CCl4 to serve as an electron trap virtually eliminates the anion bands, and further supports the anion identifications. The observed vibrational frequencies are in agreement with the results of density functional theory calculations, which predict electron affinities in the 2.8-2.4 eV range for the (H-2)ScH2, (H-2)YH2, and (H-2)LaH2 complexes, and indicate high stability for the MH4- (M = Sc, La, Y) anions and suggest the promise of synthesis on a larger scale for use as reducing agents.