Metallophilic Contacts in 2-C6F4PPh2 Bridged Heterobinuclear Complexes: A Crystallographic and Computational Study

Waechtler E, Priver SH, Wagler J, Heine T, Zhechkov L, Bennett MA, Bhargava SK (2015)

Publication Type: Journal article

Publication year: 2015

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 54

Pages Range: 6947-6957

Journal Issue: 14

DOI: 10.1021/acs.inorgchem.5b00939

Abstract

(Figure Presented) Treatment of the bis(chelate) complex trans-[Pd(κ2-2-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.

Involved external institutions

Royal Melbourne Institute of Technology (RMIT) AU Australia (AU) Technische Universität Bergakademie Freiberg DE Germany (DE) Jacobs University Bremen gGmbH DE Germany (DE) Australian National University (ANU) AU Australia (AU)

How to cite

APA:

Waechtler, E., Priver, S.H., Wagler, J., Heine, T., Zhechkov, L., Bennett, M.A., & Bhargava, S.K. (2015). Metallophilic Contacts in 2-C6F4PPh2 Bridged Heterobinuclear Complexes: A Crystallographic and Computational Study. Inorganic Chemistry, 54(14), 6947-6957. https://doi.org/10.1021/acs.inorgchem.5b00939

MLA:

Waechtler, Erik, et al. "Metallophilic Contacts in 2-C6F4PPh2 Bridged Heterobinuclear Complexes: A Crystallographic and Computational Study." Inorganic Chemistry 54.14 (2015): 6947-6957.

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