Synthesis, structure, luminescence and theorethical studies of tetranuclear gold clusters with phosphinocarborane ligands
- Calhorda, M.J. 16
- Crespo, O. 34
- Gimeno, M.C. 3
- Jones, P.G. 5
- Laguna, A. 3
- López-de-Luzuriaga, J.M. 2
- Perez, J.L. 4
- Ramón, M.A. 4
- Veiros, L.F. 1
-
1
Universidade de Lisboa
info
-
2
Universidad de La Rioja
info
-
3
Instituto de Nanociencia y Materiales de Aragón
info
-
4
Universidad de Zaragoza
info
-
5
Braunschweig University of Technology
info
-
6
Universidade Nova de Lisboa
info
ISSN: 0020-1669
Datum der Publikation: 2000
Ausgabe: 39
Nummer: 19
Seiten: 4280-4285
Art: Artikel
beta Ver similares en nube de resultadosAndere Publikationen in: Inorganic Chemistry
Zusammenfassung
Treatment of the tetranuclear gold cluster [Au4{(PPh2)2C2B9H10}2(AsPh3)2] (1), which contains the nido-carboranediphosphine [7,8-(PPh2)2C2B9H10]-, with various tertiary phosphines leads to derivatives [Au4{(PPh2)2C2B9H10}2-(PR3)2] (PR3 = PPh3 (2), P(4-MeC6H4)3 (3), P(4-OMeC6H4)3 (4)). The X-ray crystal structure of complex 4 shows a tetrahedral framework of gold atoms, two of which are chelated by the diphosphine, and two are coordinated to one monophosphine ligand each. These compounds are very stable and are obtained in high yield. MP2 calculations suggest that the two types of chemically nonequivalent gold atoms can be formally assigned as Au(I) (those attached to the arsines or phosphines) and Au(0) (those bonded to the anionic diphosphine) and emphasize the role of correlation in the gold-gold interactions. The compounds are luminescent. The emission is assigned to a gold-centered spin-forbidden transition; the assignment of the oxidation state of the gold centers on this basis leads to results coincident with those obtained by theoretical calculations.