Welsch, Stefan and Nohra, Brigitte and Peresypkina, Eugenia V. and Lescop, Christophe and Scheer, Manfred and Reau, Regis (2009) Chemistry of Bridging Phosphanes: A Comparative Study within Cu-I-Ag-I-Au-I Triad-Based Homonuclear Dimers. CHEMISTRY-A EUROPEAN JOURNAL, 15 (18). pp. 4685-4703. ISSN 0947-6539, 1521-3765
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Bis(2-pyridyl)phosphole C reacted with AgPF6 and dppm giving rise to dicationic dimer 1. in which C acts as a 1 kappa N:1,2 kappa P:2 kappa N-donor with a symmetrically bridging P-centre. This complex gives the first example of dimers based on trigonal planar metal centres bearing a bridging sigma(3),lambda(3)-phosphane ligand. The reaction of two equivalents of C with AgPF6 and Ag{Al[OC(CF3)(3)](4)} afforded dicationic dimers 2 and 3 of general formula Ag-2(C)(2)(2+), respectively. X-ray diffraction studies showed that one ligand C acts as a 1 kappa N:1,2 kappa P:2 kappa N-donor with a symmetrically bridging P-centre and one behaves as a 1 kappa N:2 kappa P-chelate. In complex 3, one toluene molecule interacts with an Ag centre, giving the first example of a mixed coordination dimer featuring a bridging P-donor. Ag(I-)dimers 4a-c of the general formula Ag-2(C)(3)(2+), 2 X- (X=PF6, BF4, Al[OC- (CF3)(3)](4)) have been prepared according to different routes and characterised by X-ray diffraction study. In these derivatives, C exhibits a variety of coordination modes depending oil the nature of the counteranion and of the solvent molecules included in the asymmetric units. These complexes call feature 0, 1 or 2 bridging P-donors. These results definitively demonstrate that the P-centre of phosphane ligands can easily switch from a bridging to a semi-bridging and a non-bridging coordination mode. Dimer 2 is used as an "adaptive" molecular clip for the synthesis of pi-stacked metallocyclophanes 7a,b and 8 upon reaction with ditopic linkers. X-ray diffraction studies revealed that these supramolecular species behave as receptors for the counteranions (PF6, BF4) and that the nature of the anion impacts the stereochemistry of the supramolecular metallocyclophanes. Au-I-Dimers 10a,b bearing two ligands C acting as 1 kappa N:2 kappa P-chelates are prepared and characterised in the solid-state.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DINUCLEAR RHODIUM COMPLEXES; WEAKLY COORDINATING ANIONS; NONCLASSICAL BONDING MODES; X-RAY; STRUCTURAL-CHARACTERIZATION; PALLADIUM(I) DIMERS; TERTIARY PHOSPHANES; MOLECULAR-STRUCTURE; CONJUGATED SYSTEMS; CRYSTAL-STRUCTURE; bridging ligands; coordination modes; gold; P ligands; silver |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 12 Oct 2020 05:36 |
| Last Modified: | 12 Oct 2020 05:36 |
| URI: | https://pred.uni-regensburg.de/id/eprint/29668 |
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