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Title: Search for Osme Bonds with π Systems as Electron Donors
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.  more » « less
Award ID(s):
1954310
PAR ID:
10520813
Author(s) / Creator(s):
; ;
Publisher / Repository:
mdpi
Date Published:
Journal Name:
Molecules
Volume:
29
Issue:
1
ISSN:
1420-3049
Page Range / eLocation ID:
79
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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