Structures and Stability of Mixed Main Group Hydrides [PBEH6]n (E = C, Si, Ge; n = 1-4) and Donor-Acceptor Stabilization of Monomeric Chain Isomers

Anna M Belousova; Alexey Y Timoshkin

doi:10.1021/acs.jpca.3c04179

Structures and Stability of Mixed Main Group Hydrides [PBEH₆]_n (E = C, Si, Ge; n = 1-4) and Donor-Acceptor Stabilization of Monomeric Chain Isomers

J Phys Chem A. 2023 Sep 7;127(35):7353-7363. doi: 10.1021/acs.jpca.3c04179. Epub 2023 Aug 24.

Authors

Anna M Belousova¹, Alexey Y Timoshkin¹

Affiliation

¹ Institute of Chemistry, St. Petersburg State University, Universitetskaya emb. 7/9, 199034, St. Petersburg, Russia.

PMID: 37615426
DOI: 10.1021/acs.jpca.3c04179

Abstract

Structures and stability of mixed group 13-14-15 element hydrides PBEH₆ (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)₅ and trimethylamine provides a synergetic effect, allowing stabilization of 13-14-15 chain compounds.