KReH晶体中ReH的异常分子内运动：计算研究揭示的圆圈舞和三臂旋转门机制

Unusual Intramolecular Motion of ReH in KReH Crystal: Circle Dance and Three-Arm Turnstile Mechanisms Revealed by Computational Studies.

作者信息

Tao Yunwen, Wang Xianlong, Zou Wenli, Luo Geng-Geng, Kraka Elfi

机构信息

Department of Chemistry, Southern Methodist University, 3215 Daniel Avenue, Dallas, Texas 75275-0314, United States.

Department of Bioinformatics, School of Medical Technology and Engineering, Key Laboratory of Medical Bioinformatics, Key Laboratory of Ministry of Education for Gastrointestinal Cancer, Fujian Medical University, Fuzhou 350122, P. R. China.

出版信息

Inorg Chem. 2022 Jan 17;61(2):1041-1050. doi: 10.1021/acs.inorgchem.1c03118. Epub 2021 Dec 29.

DOI:10.1021/acs.inorgchem.1c03118

PMID:34965110

Abstract

The nonahydridorhenate dianion ReH is a unique rhenium polyhydride complex due to its remarkably high coordination number; however, its detailed polytopal rearrangement process in either solution or crystal is so far unclear. In this work, our quantum chemical calculations have identified two previously unreported fluxional mechanisms for the ReH dianion in the KReH crystal: three-arm turnstile rotation and circle dance mechanism. These two polytopal rearrangements in the crystal offer an alternative interpretation to the pulse and wide-line NMR spectra (Farrar et al. . , 51, 3595). The previously postulated hindered rotation of the whole ReH dianion in KReH (White et al. , 68, 1414) turns out to be a combination of the above-mentioned two elementary fluxional processes. In addition, our calculations have confirmed the Muetterties' ⇌ rearrangement as the intramolecular motion for the ReH dianion in solution.

摘要

九氢铼酸二价阴离子ReH₉²⁻是一种独特的铼多氢配合物，因其具有极高的配位数；然而，到目前为止，其在溶液或晶体中的详细多面体重排过程尚不清楚。在这项工作中，我们的量子化学计算确定了KReH₉晶体中ReH₉²⁻的两种先前未报道的动态机制：三臂旋转门旋转和圆圈舞机制。晶体中的这两种多面体重排为脉冲和宽线核磁共振谱提供了另一种解释（Farrar等人，《美国化学会志》，51, 3595）。先前假设的KReH₉中整个ReH₉²⁻的受阻旋转（White等人，《无机化学》，68, 1414）原来是上述两种基本动态过程的组合。此外，我们的计算证实了Muetterties的⇌重排是溶液中ReH₉²⁻的分子内运动。