Synthesis, structure, luminescence and theorethical studies of tetranuclear gold clusters with phosphinocarborane ligands

  1. Calhorda, M.J. 16
  2. Crespo, O. 34
  3. Gimeno, M.C. 3
  4. Jones, P.G. 5
  5. Laguna, A. 3
  6. López-de-Luzuriaga, J.M. 2
  7. Perez, J.L. 4
  8. Ramón, M.A. 4
  9. Veiros, L.F. 1
  1. 1 Universidade de Lisboa
    info

    Universidade de Lisboa

    Lisboa, Portugal

    ROR https://ror.org/01c27hj86

  2. 2 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  3. 3 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

  4. 4 Universidad de Zaragoza
    info

    Universidad de Zaragoza

    Zaragoza, España

    ROR https://ror.org/012a91z28

  5. 5 Braunschweig University of Technology
    info

    Braunschweig University of Technology

    Brunswick, Alemania

    ROR https://ror.org/010nsgg66

  6. 6 Universidade Nova de Lisboa
    info

    Universidade Nova de Lisboa

    Lisboa, Portugal

    ROR https://ror.org/02xankh89

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Revista:
Inorganic Chemistry

ISSN: 0020-1669

Año de publicación: 2000

Volumen: 39

Número: 19

Páginas: 4280-4285

Tipo: Artículo

DOI: 10.1021/IC000136Y SCOPUS: 2-s2.0-0034683473 WoS: WOS:000089457100015 GOOGLE SCHOLAR

Otras publicaciones en: Inorganic Chemistry

Repositorio institucional: lock_openAcceso abierto Editor

Resumen

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.