title: Theoretical Evidence for Transannular Metal-Metal Interactions in Dinuclear Coinage Metal Complexes.
abstract: The dinuclear head-to-tail complexes [M(2)(PPh(2)CH(2)SPh)(2)](2+) (M = Cu (1), Ag (2a, 2b), Au (4)) are obtained either by reaction of [Cu(CH(3)CN)(4)]CF(3)SO(3), AgClO(4), AgCF(3)SO(3), with equimolecular amounts of PPh(2)CH(2)SPh or of [AuCl(PPh(2)CH(2)SPh)] (3), prepared by reaction of [AuCl(tht)] and PPh(2)CH(2)SPh, with AgCF(3)SO(3). 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 [M(2)(H(2)PCH(2)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.
authors.affiliation: Institut für Anorganische und Analytische Chemie der Technischen Universität, Postfach 3329, D-38023 Braunschweig, Germany.
authors.forename: Eduardo J.
authors.initials: EJ
authors.lastname: Fernández
authors.forename: José M.
authors.initials: JM
authors.lastname: López-De-Luzuriaga
authors.forename: Miguel
authors.initials: M
authors.lastname: Monge
authors.forename: Miguel A.
authors.initials: MA
authors.lastname: Rodríguez
authors.forename: Olga
authors.initials: O
authors.lastname: Crespo
authors.forename: M. Concepción
authors.initials: MC
authors.lastname: Gimeno
authors.forename: Antonio
authors.initials: A
authors.lastname: Laguna
authors.forename: Peter G.
authors.initials: PG
authors.lastname: Jones