| Autor: |
de Azevedo Santos, Lucas, Wagner, Timon, Visscher, Klaas, Nitsch, Jörn, Bickelhaupt, F. Matthias, Fonseca Guerra, Célia |
| Zdroj: |
Physical Chemistry Chemical Physics (PCCP); 8/21/2024, Vol. 26 Issue 31, p20928-20936, 9p |
| Abstrakt: |
We have quantum chemically analyzed the closed-shell d8–d8 metallophilic interaction in dimers of square planar [M(CO)2X2] complexes (M = Ni, Pd, Pt; X = Cl, Br, I) using dispersion-corrected density functional theory at ZORA-BLYP-D3(BJ)/TZ2P level of theory. Our purpose is to reveal the nature of the [X2(CO)2M]⋯[M(CO)2X2] bonding mechanism by analyzing trends upon variations in M and X. Our analyses reveal that the formation of the [M(CO)2X2]2 dimers is favored by an increasingly stabilizing electrostatic interaction when the M increases in size and by more stabilizing dispersion interactions promoted by the larger X. In addition, there is an overlooked covalent component stemming from metal–metal and ligand–ligand donor–acceptor interactions. Thus, at variance with the currently accepted picture, the d8–d8 metallophilicity is attractive, and the formation of [M(CO)2X2]2 dimers is not a purely dispersion-driven phenomenon. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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