Belousova Anna M, Timoshkin Alexey Y
Institute of Chemistry, St. Petersburg State University, Universitetskaya emb. 7/9, 199034, St. Petersburg, Russia.
J Phys Chem A. 2023 Sep 7;127(35):7353-7363. doi: 10.1021/acs.jpca.3c04179. Epub 2023 Aug 24.
Structures and stability of mixed group 13-14-15 element hydrides PBEH (E = C, Si, Ge), their oligomers, and complexes with Lewis acids and Lewis base are computationally studied at the B3LYP-D3/def2-TZVP level of theory. Unsubstituted chain hydrides are unstable and are expected to form cyclic oligomers. Cyclization can be prevented by the donor-acceptor complex formation. For complexes of chain hydrides with Lewis acid in many cases additional reactivity beyond the donor-acceptor complex formation is observed: cyclization and migration of terminal group from the group 13 Lewis acid to the boron or group 14 terminal atoms of the hydride. The most promising compounds for the experimental studies have been identified. Joint stabilization by both W(CO) and trimethylamine provides a synergetic effect, allowing stabilization of 13-14-15 chain compounds.
在B3LYP-D3/def2-TZVP理论水平上，对混合的13-14-15族元素氢化物PBEH（E = C、Si、Ge）及其低聚物以及与路易斯酸和路易斯碱的配合物的结构和稳定性进行了计算研究。未取代的链状氢化物不稳定，预计会形成环状低聚物。供体-受体配合物的形成可以阻止环化。在许多情况下，对于链状氢化物与路易斯酸的配合物，观察到除了形成供体-受体配合物之外还有额外的反应性：环化以及末端基团从13族路易斯酸迁移到氢化物的硼或14族末端原子上。已经确定了最有希望用于实验研究的化合物。W(CO)和三甲胺的联合稳定作用提供了协同效应，使得13-14-15链状化合物得以稳定。
