Wang Xuefeng, Andrews Lester
Department of Chemistry, University of Virginia, Charlottesville, 22904-4319, USA.
Inorg Chem. 2005 Oct 3;44(20):7189-93. doi: 10.1021/ic050614a.
Laser-ablated Hf atoms react with H2O2 and with H2 + O2 mixtures in solid argon to form the Hf(OH)2 and Hf(OH)4 molecules, which are identified from the effect of isotopic substitution on the matrix infrared spectra. Electronic structure calculations at the MP2 level varying all bond lengths and angles converge to nearly linear and tetrahedral molecules, respectively, and predict frequencies for these new product molecules and mixed isotopic substituted molecules of lower symmetry that are in excellent agreement with observed values, which confirms the identification of these hafnium hydroxide molecules. This work provides the first evidence for a metal tetrahydroxide molecule and shows that the metal atom reaction with H2O2 in excess argon can be used to form pure metal tetrahydroxide molecules, which are not stable in the solid state.
在固态氩中，激光烧蚀的铪原子与过氧化氢以及氢气和氧气的混合物发生反应，形成Hf(OH)₂和Hf(OH)₄分子，这些分子可通过同位素取代对基质红外光谱的影响来识别。在MP2水平上进行的电子结构计算，改变所有键长和键角，分别收敛到接近线性和四面体的分子，并预测这些新产物分子以及对称性较低的混合同位素取代分子的频率，这些频率与观测值高度吻合，这证实了这些氢氧化铪分子的识别。这项工作为金属四氢氧化物分子提供了首个证据，并表明在过量氩气中金属原子与过氧化氢的反应可用于形成纯金属四氢氧化物分子，这些分子在固态时不稳定。
