Density functional (DFT) studies and hybrid QM/MM-DFT calculations demonstrate the importance of pi-pi stacking interactions in determining the structural features of two exemplary d(8) palladium complexes, PdBr(p-NCC6H4)({S}-MeO-Biphep), 1, and PdBr(C6F5)-({S}-MeO-Biphep), 2. Despite the superficial similarity of the two compounds, the former shows marked distortions from square planar geometry, while the latter exhibits an almost ideal structure. Attractive pi-pi stacking interactions between two pairs of P-phenyl rings and the arene backbone of the MeO-Biphep are the main origin of the distortion in complex 1. The planar structure of complex 2 is preferred as a consequence of an additional stacking interaction between one P-phenyl ring and the pentafluorophenyl a-ligand. The artificial introduction of an analogous stacking interaction in complex 1 reestablishes an ideal square planar geometry, thus demonstrating that switching on/off specific pi-pi interactions distinctly alters the coordination geometry. These results reveal a previously unrecognized role for pi-pi stacking interactions in the stabilization of structural features in transition metal compounds. This suggests pi-pi stacking interactions as a potential new design principle in tailoring coordination compounds.
The role of pi-pi, stacking interactions in square planar palladium complexes : combined quantum mechanics/molecular mechanics QM/MM studies / A. Magistrato, P. Pregosin, A. Albinati, U. Rothlisberger. - In: ORGANOMETALLICS. - ISSN 0276-7333. - 20:20(2001), pp. 4178-4184.
The role of pi-pi, stacking interactions in square planar palladium complexes : combined quantum mechanics/molecular mechanics QM/MM studies
A. AlbinatiPenultimo
;
2001
Abstract
Density functional (DFT) studies and hybrid QM/MM-DFT calculations demonstrate the importance of pi-pi stacking interactions in determining the structural features of two exemplary d(8) palladium complexes, PdBr(p-NCC6H4)({S}-MeO-Biphep), 1, and PdBr(C6F5)-({S}-MeO-Biphep), 2. Despite the superficial similarity of the two compounds, the former shows marked distortions from square planar geometry, while the latter exhibits an almost ideal structure. Attractive pi-pi stacking interactions between two pairs of P-phenyl rings and the arene backbone of the MeO-Biphep are the main origin of the distortion in complex 1. The planar structure of complex 2 is preferred as a consequence of an additional stacking interaction between one P-phenyl ring and the pentafluorophenyl a-ligand. The artificial introduction of an analogous stacking interaction in complex 1 reestablishes an ideal square planar geometry, thus demonstrating that switching on/off specific pi-pi interactions distinctly alters the coordination geometry. These results reveal a previously unrecognized role for pi-pi stacking interactions in the stabilization of structural features in transition metal compounds. This suggests pi-pi stacking interactions as a potential new design principle in tailoring coordination compounds.File | Dimensione | Formato | |
---|---|---|---|
om010485f.pdf
accesso riservato
Tipologia:
Publisher's version/PDF
Dimensione
133.75 kB
Formato
Adobe PDF
|
133.75 kB | Adobe PDF | Visualizza/Apri Richiedi una copia |
Pubblicazioni consigliate
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.