title: Metallophilic Contacts in 2-C6F4PPh2 Bridged Heterobinuclear Complexes: A Crystallographic and Computational Study.
abstract: Treatment of the bis(chelate) complex trans-[Pd(κ(2)-2-C6F4PPh2)2] (7) with PMe3 gave trans-[Pd(κC-2-C6F4PPh2)2(PMe3)2] (13) as a mixture of syn- and anti-isomers. Reaction of 13 with CuCl, AgCl, or [AuCl(tht)] (tht = tetrahydrothiophene) gave the heterobinuclear complexes [(Me3P)2Pd(μ-2-C6F4PPh2)2MCl] [M = Cu (14), Ag (15), Au (16)], from which the corresponding salts [(Me3P)2Pd(μ-2-C6F4PPh2)2M]PF6 [M = Cu (17), Ag (18), Au (19)] could be prepared by abstraction of the chloro ligand with TlPF6; 18, as well as its triflato (20) and trifluoroacetato (21) analogues, were also prepared directly from 13 and the appropriate silver salt. Reaction of 13 with [AuCl(PMe3)] gave the zwitterionic complex [(Me3P)PdCl(μ-2-C6F4PPh2)2Au] (24) in which the 2-C6F4PPh2 ligands are in a head-to-head arrangement. In contrast, the analogous reaction with [AuCl(PPh3)] gave [(Ph3P)PdCl(μ-2-C6F4PPh2)2Au] (25) with a head-to-tail ligand arrangement. Single crystal X-ray diffraction studies of complexes 14-21 show short metal-metal separations [2.7707(11)-2.9423(3) Å] suggestive of attractive noncovalent (dispersion) interactions, a conclusion that is supported by theoretical calculations of the electron localization function and the noncovalent interactions descriptor.
authors.affiliation: †Centre for Advanced Materials and Industrial Chemistry (CAMIC), School of Applied Sciences (Applied Chemistry), RMIT University, GPO Box 2476 V, Melbourne, Victoria 3001, Australia.|‡Institut für Anorganische Chemie, Technische Universität Bergakademie Freiberg, 09596 Freiberg, Germany.
authors.forename: Erik
authors.initials: E
authors.lastname: Wächtler
authors.affiliation: †Centre for Advanced Materials and Industrial Chemistry (CAMIC), School of Applied Sciences (Applied Chemistry), RMIT University, GPO Box 2476 V, Melbourne, Victoria 3001, Australia.
authors.forename: Steven H
authors.initials: SH
authors.lastname: Privér
authors.affiliation: ‡Institut für Anorganische Chemie, Technische Universität Bergakademie Freiberg, 09596 Freiberg, Germany.
authors.forename: Jörg
authors.initials: J
authors.lastname: Wagler
authors.affiliation: §Centre for Functional Nanomaterials (Nanofun), Engineering and Science, Jacobs University, 28759 Bremen, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Heine
authors.affiliation: §Centre for Functional Nanomaterials (Nanofun), Engineering and Science, Jacobs University, 28759 Bremen, Germany.
authors.forename: Lyuben
authors.initials: L
authors.lastname: Zhechkov
authors.affiliation: ∥Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 2601, Australia.
authors.forename: Martin A
authors.initials: MA
authors.lastname: Bennett
authors.affiliation: †Centre for Advanced Materials and Industrial Chemistry (CAMIC), School of Applied Sciences (Applied Chemistry), RMIT University, GPO Box 2476 V, Melbourne, Victoria 3001, Australia.
authors.forename: Suresh K
authors.initials: SK
authors.lastname: Bhargava