Volkov Mikhail A, Novikov Anton P, Borisova Nataliya E, Grigoriev Mikhail S, German Konstantin E
Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences, 31 Bldg 4, Leninsky Prosp., Moscow 119071, Russian Federation.
Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow119991, Russian Federation.
Inorg Chem. 2023 Aug 21;62(33):13485-13494. doi: 10.1021/acs.inorgchem.3c01863. Epub 2023 Aug 10.
The first polyoxorhenate(VII) compound, pyrazolium polyoxorhenate ((CNH)ReO), and two new rhenium(VII) and technetium(VII) salts have been synthesized and studied. The structure of TcO has been reinvestigated. The [ReO] polyoxoanion contains four Re(VII) atoms: one with an octahedral environment and three with a tetrahedral environment. Polyoxorhenate is formed in the presence of a buffering agent, pyrazole, the latter maintaining pH = 2.5 during the formation of crystals. The [ReO] polyoxoanion has novel stoichiometry and the -conformation, likely due to the stabilizing intramolecular nonvalence interactions. For the first time, intramolecular interactions of the Re···O, Re···μ-O, and O···O are described (previously known were only intermolecular ones). In all of the compounds, intermolecular Re···O interactions are observed, which, however, in other compounds, do not lead to the formation of polyoxometalates. The Hirshfeld surface analysis showed that the main contribution to intermolecular interactions is made by the O···H/H···O contacts, van der Waals interactions of the H···H for cations, and the O···O for anions. DFT calculations of the [ReO] geometry, compared with the crystallographic data, revealed a deviation in the angles. Mass spectroscopy of the red polyoxometalate [TcO] was carried out for the first time. Comparison of the results of MALDI and LI for the first known polyoxometalates of the manganese subgroup made it possible to find general patterns of oligomerization for rhenium and technetium compounds. The ESI-MS and LI-MS methods applied to solution and crystals Re compounds made it possible to prove rhenium being able to form not only [ReO] but also heavier polyoxoanions.
首个聚氧铼（VII）化合物——吡唑鎓聚氧铼酸盐（(CNH)ReO），以及两种新的铼（VII）和锝（VII）盐已被合成并研究。对TcO的结构进行了重新研究。[ReO]聚氧阴离子包含四个Re（VII）原子：一个处于八面体环境，三个处于四面体环境。聚氧铼酸盐在缓冲剂吡唑存在的情况下形成，后者在晶体形成过程中维持pH = 2.5。[ReO]聚氧阴离子具有新颖的化学计量比和构象，这可能归因于稳定的分子内非价相互作用。首次描述了Re···O、Re···μ - O和O···O的分子内相互作用（此前已知的只有分子间相互作用）。在所有化合物中都观察到了分子间的Re···O相互作用，然而，在其他化合物中，这种相互作用不会导致多金属氧酸盐的形成。Hirshfeld表面分析表明，分子间相互作用的主要贡献来自O···H/H···O接触、阳离子的H···H范德华相互作用以及阴离子的O···O相互作用。与晶体学数据相比，[ReO]几何结构的密度泛函理论计算揭示了角度上的偏差。首次对红色多金属氧酸盐[TcO]进行了质谱分析。对锰族首个已知多金属氧酸盐的基质辅助激光解吸电离（MALDI）和激光电离（LI）结果进行比较，使得能够找到铼和锝化合物低聚的一般模式。应用于溶液和晶体Re化合物的电喷雾电离质谱（ESI - MS）和激光电离质谱（LI - MS）方法使得能够证明铼不仅能够形成[ReO]，还能形成更重的聚氧阴离子。
