Document Type
Article
Author ORCID Identifier
Qingzhong Li https://orcid.org/0000-0002-0511-0167
Steve Scheiner https://orcid.org/0000-0003-0793-0369
Journal/Book Title
Molecules
Publication Date
12-22-2023
Publisher
MDPI AG
Volume
29
Issue
1
First Page
1
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.
Last Page
11
Abstract
The Osme bond is defined as pairing a Group 8 metal atom as an electron acceptor in a noncovalent interaction with a nucleophile. DFT calculations with the ωB97XD functional consider MO4 (M = Ru, Os) as the Lewis acid, paired with a series of π electron donors C2H2 , C2H4 , C6H6 , C4H5N, C4H4O, and C4H4S. The calculations establish interaction energies in the range between 9.5 and 26.4 kJ/mol. Os engages in stronger interactions than does Ru, and those involving more extensive π-systems within the aromatic rings form stronger bonds than do the smaller ethylene and acetylene. Extensive analysis questions the existence of a true Osme bond, as the bonding chiefly involves interactions with the three O atoms of MO4 that lie closest to the π-system, via π(C-C)→σ*(M-O) transfers. These interactions are supplemented by back donation from M-O bonds to the π*(CC) antibonding orbitals of the π-systems. Dispersion makes a large contribution to these interactions, higher than electrostatics and much greater than induction.
Recommended Citation
Wang, X.; Li, Q.; Scheiner, S. Search for Osme Bonds with π Systems as Electron Donors. Molecules 2024, 29, 79. https://doi.org/10.3390/molecules29010079
