Metallophilic contacts in 2-C6F4PPh2 bridged heterobinuclear complexes: a crystallographic and computational study.

Wächtler, E, Priver, S, Wagler, J, Heine, T, Zhechkov, L, Bennett, M and Bhargava, S 2015, 'Metallophilic contacts in 2-C6F4PPh2 bridged heterobinuclear complexes: a crystallographic and computational study.', Inorganic Chemistry, vol. 54, pp. 6947-6957.


Document type: Journal Article
Collection: Journal Articles

Title Metallophilic contacts in 2-C6F4PPh2 bridged heterobinuclear complexes: a crystallographic and computational study.
Author(s) Wächtler, E
Priver, S
Wagler, J
Heine, T
Zhechkov, L
Bennett, M
Bhargava, S
Year 2015
Journal name Inorganic Chemistry
Volume number 54
Start page 6947
End page 6957
Total pages 11
Publisher American Chemical Society
Abstract Treatment of the bis(chelate) complex trans-[Pd(kappa(2)-2-C6F4PPh2)2] (7) with PMe3 gave trans-[Pd(kappaC-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(mu-2-C6F4PPh2)2MCl] [M = Cu (14), Ag (15), Au (16)], from which the corresponding salts [(Me3P)2Pd(mu-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(mu-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(mu-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) A] suggestive of attractive noncovalent (dispersion) interactions, a conclusion that is supported by theoretical calculations of the electron localization function and the noncovalent interactions descriptor.
Subject Organometallic Chemistry
DOI - identifier 10.1021/acs.inorgchem.5b00939
Copyright notice © 2015 American Chemical Society
ISSN 1520-510X
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