同配四氢金属酸根阴离子MH₄⁻（M = Sc、Y、La）。基质红外光谱和密度泛函理论计算
Homoleptic tetrahydrometalate anions MH(4)(-) (M = Sc, Y, La). Matrix infrared spectra and DFT calculations.
作者信息
Wang Xuefeng, Andrews Lester
机构信息
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, USA.
出版信息
J Am Chem Soc. 2002 Jun 26;124(25):7610-3. doi: 10.1021/ja020112l.
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 MH(2) and (H(2))MH(2). The homoleptic tetrahydrometalate anions ScH(4)(-), YH(4)(-), and LaH(4)(-) are formed by electron capture and identified by isotopic substitution (D(2), HD, and H(2) + D(2) mixtures). Doping with CCl(4) 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))ScH(2), (H(2))YH(2), and (H(2))LaH(2) complexes, and indicate high stability for the MH(4)(-) (M = Sc, La, Y) anions and suggest the promise of synthesis on a larger scale for use as reducing agents.
激光烧蚀的钪（Sc）、钇（Y）和镧（La）原子在过量的氩气、氖气和氘气中冷凝时与分子氢发生反应，生成金属二氢化物分子以及二氢配合物MH₂和(H₂)MH₂。通过电子俘获形成同配四氢金属酸根阴离子ScH₄⁻、YH₄⁻和LaH₄⁻，并通过同位素取代（D₂、HD以及H₂ + D₂混合物）对其进行鉴定。用CCl₄作为电子陷阱进行掺杂实际上消除了阴离子谱带，进一步支持了对阴离子的鉴定。观察到的振动频率与密度泛函理论计算结果一致，该计算预测(H₂)ScH₂、(H₂)YH₂和(H₂)LaH₂配合物的电子亲和能在2.8 - 2.4 eV范围内，并表明MH₄⁻（M = Sc、La、Y）阴离子具有高稳定性，这暗示了大规模合成用作还原剂的前景。
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