ISSN:
0009-2940
Keywords:
Silver(I) sandwich complexes
;
Crown dithioethers, unsaturated
;
Bis(methylthio)maleonitrile
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The coordination chemistry of the four oxa-crowned derivatives of dithiomaleonitrile mn-12S2O2, mn-15S2O3, mn-18S2O4, and mn-21S2O5 as well as of the acyclic bis(methylthio)maleonitrile mn-S2 with AgI was investigated by X ray structural and spectroscopic methods. The 2:1 complexes (ligand/AgI) [Ag(mn-12S2O2)2]PF6, [1]PF6, [Ag(mn-15S2O3)2]PF6, [2]PF6, and [Ag(mn-S2)2]PF6, [6]PF6, and the 1:1 complexes [Ag(mn-15S2O3)]ClO4, [3]ClO4, [Ag(mn-18S2O4)]PF6, [4]PF6, and [Ag(mn-21S2O5)]PF6 [5]PF6, were obtained with AgPF6 or AgClO4 in MeOH. The stoichiometry of the macrocyclic AgI complexes and the coordination mode of mn-S2On+1 coronands (n = 1-4) is determined by the length of the macrocyclic oligoethylene chain. - The mn-crown dithioethers mn-12S2O2 and mn-15S2O3 form with AgPF6 the new sandwich complexes [Ag(mn-12S2O2)2]PF6, [1]PF6, and [Ag(mn-15S2O3)2]PF6, [2]PF6. [1]PF6 crystallises in the triclinic space group P1. In the centrosymmetric cation [1]+ each mn-12S2O2 ligand is coordinated to the AgI centre in an endo manner via both S atoms and one O atom. The distance of the second O atom of mn-12S2O2 to AgI is somewhat longer than a normal Ag-Oether bond. The overall environment around AgI in [1]+ is that of a distorted cubic S4O4 set of donors. [2]PF6 crystallises in the monoclinic space group C2/c. In the centrosymmetric cation [2]+ silver(I) is planar-coordinated by the four S atoms of both mn-15S2O3 molecules. The six O atoms of both mn-15S2O3 ligands show only long-range interactions to the AgI ion. They surround AgI almost vertically to the planar S4 set of donors in a crown-like manner. - The crystal structures of the 1:1 complexes [Ag(mn-18S2O4)]PF6, [4]PF6, and [Ag(mn-21S2O5)]PF6, [5]PF6, consist of linear chain polymers. [5]PF6 forms an N-bridged chain polymer of endocyclic [Ag(mn-21S2O5)]+ units with S1O4NNitrile coordination at the AgI centre. In the 2:1 complex [Ag(mn-S2)2]PF6, [6]PF6, each mn-S2 acts as a monodentate NNitrile donor. - 13C-NMR studies in nitromethane solution confirm that the AgI ions in the complexes of the mn-crown dithioethers remain coordinated. However, the AgI ion in complex of mn-S2 is decoordinated.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19961290711
