Vent-Schmidt Thomas, Andrews Lester, Thanthiriwatte K Sahan, Dixon David A, Riedel Sebastian
Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg , Albertstraße 21, D-79104 Freiburg i. Br., Germany.
Department of Chemistry, University of Virginia , P.O. Box 400319, Charlottesville, Virginia 22904-4319, United States.
Inorg Chem. 2015 Oct 19;54(20):9761-9. doi: 10.1021/acs.inorgchem.5b01383. Epub 2015 Sep 29.
The compounds H2ThSe and H2USe were synthesized by the reaction of laser-ablated actinide metal atoms with H2Se under cryogenic conditions following the procedures used to synthesize H2AnX (An = Th, U; X = O, S). The molecules were characterized by infrared spectra in an argon matrix with the aid of deuterium substitution and electronic structure calculations at the density functional theory level. The main products, H2ThSe and H2USe, are shown to have a highly polarized actinide-selenium triple bond, as found for H2AnS on the basis of electronic structure calculations. There is an even larger back-bonding of the Se with the An than found for the corresponding sulfur compounds. These molecules are of special interest as rare examples of multiple bonding of selenium to a metal, particularly an actinide metal.
化合物H₂ThSe和H₂USe是通过在低温条件下，使激光烧蚀的锕系金属原子与H₂Se反应合成的，采用的是用于合成H₂AnX（An = Th，U；X = O，S）的程序。借助氘代和密度泛函理论水平的电子结构计算，在氩气基质中通过红外光谱对分子进行了表征。基于电子结构计算，主要产物H₂ThSe和H₂USe显示出具有高度极化的锕系 - 硒三键，正如在H₂AnS中发现的那样。与相应的硫化合物相比，Se与An之间存在更大的反馈键。作为硒与金属，特别是与锕系金属多重键合的罕见例子，这些分子具有特殊的研究意义。
