Theoretical evidence for transannular metal-metal interactions in dinuclear coinage metal complexes

  1. Fernández, E.J. 1
  2. López-de-Luzuriaga, J.M. 1
  3. Monge, M. 1
  4. Rodríguez, M.A. 1
  5. Crespo, O. 2
  6. Gimeno, M.C. 2
  7. Laguna, A. 2
  8. Jones, P.G. 3
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

  3. 3 Braunschweig University of Technology
    info

    Braunschweig University of Technology

    Brunswick, Alemania

    ROR https://ror.org/010nsgg66

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Revista:
Inorganic Chemistry

ISSN: 0020-1669

Año de publicación: 1998

Volumen: 37

Número: 23

Páginas: 6002-6006

Tipo: Artículo

DOI: 10.1021/IC980786Q SCOPUS: 2-s2.0-0037747607 WoS: WOS:000077072900007 GOOGLE SCHOLAR

Otras publicaciones en: Inorganic Chemistry

Repositorio institucional: lock_openAcceso abierto Editor

Resumen

The dinuclear head-to-tail complexes [M2(PPh2CH2SPh)2]2- (M = Cu (1), Ag (2a, 2b), Au (4)) are obtained either by reaction of [Cu(CH3CN)4]CF3SO3, AgClO4, AgCF3SO3, with equimolecular amounts of PPh2CH2SPh or of [AuCl(PPh2CH2SPh)] (3), prepared by reaction of [AuCl(tht)] and PPh2CH2SPh, with AgCF3SO3. The crystal structures of complexes 2a and 4 have been established by X-ray diffraction studies. Ab initio HF/II and MP2/II calculations have been performed on the [M2(H2PCH:SH)2]2+ model, indicating that metallophilic attraction is indeed present for all the coinage metals as a correlation effect and is strengthened in the case of gold by relativistic effects. Since experimental and theoretically predicted geometries are in close agreement, we assume that our calculations are accurate enough to obtain valid conclusions.