Wang Xuefeng, Andrews Lester
Department of Chemistry, University of Virginia, P.O. Box 400319, Charlottesville, Virginia 22904-4319, USA.
Inorg Chem. 2008 Sep 15;47(18):8159-66. doi: 10.1021/ic800552s. Epub 2008 Aug 12.
Laser ablated chromium, molybdenum, and tungsten atoms react with germane during condensation in excess noble gases. The chromium reaction stopped at the germyl metal hydride, molybdenum gave some hydride but mostly germylidyne, and tungsten reacted spontaneously to give only the germylidyne species. These molecules were identified by isotopic shifts, density-functional theory product energy and frequency calculations, and comparison to the analogous methane and silane reaction products. Effective bond orders for the HGe[triple bond]MoH3 and HGe[triple bond]WH3 molecules are 2.82 and 2.87 using the B3LYP density functional, and are slightly lower than their silicon and carbon analogues. Our calculated Ge[triple bond]M triple bond lengths for these simple trihydride complexes are 0.05 to 0.10 A shorter than those measured for larger group 6 organometallic complexes.
激光烧蚀的铬、钼和钨原子在过量稀有气体中冷凝时与锗烷发生反应。铬的反应在锗基金属氢化物处停止，钼生成了一些氢化物，但主要是次锗炔，而钨自发反应仅生成次锗炔物种。这些分子通过同位素位移、密度泛函理论产物能量和频率计算以及与类似的甲烷和硅烷反应产物进行比较来鉴定。使用B3LYP密度泛函，HGe≡MoH₃和HGe≡WH₃分子的有效键级分别为2.82和2.87，略低于它们的硅和碳类似物。我们计算出的这些简单三氢化物配合物的Ge≡M三键长度比为较大的第6族有机金属配合物测得的长度短0.05至0.10埃。
