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Structural and infrared spectroscopic studies of some novel mechanochemically accessed adducts of silver(I) oxoanion salts with thiourea

Inorganic Chemistry, ISSN: 0020-1669, Vol: 48, Issue: 7, Page: 3185-3197
2009
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An investigation of the silver(l) nitrate/thiourea ("tu") system, exploiting the uniquely powerful access provided by the recently developed combination of mechanochemical synthesis coupled with Vibrational Spectroscopy, has resulted in the identification of solid adducts AgN /tu (x.γ) for x:y= 1:1,1:1.5,15:23 (= 1:1.5333), and 1:3. This contrasts with previously published claims for the existence of 1:2 and 1:4 complexes and was confirmed in the case of the 1:3 and 15:23 complexes by X-ray crystal structure determinations on samples prepared by crystallization from aqueous solution. The 1:3 sulfate and perchlorate complexes were also prepared for comparison with the corresponding nitrate compound. In the 1:3 nitrate complex, the one independent silver atom major component (0.78(1)) is closely trigonal planar AgS (Ag-S 2.518(2)-2.592(1) Å, Σ(S-Ag-S) 359.7 ); there are minor nearby components (0.11(1)) which may be regarded as four-coordinate, forming a putative one-dimensional polymer. The sulfate, obtained as its tetrahydrate, has a cation of the familiar binuclear form [{(tu) Ag(μ-S-tu)} ](S0 ) . 4H 0, while the perchlorate, previously also characterized with the binuclear cation in the anhydrate, has now been isolated as the hemihydrate, having a single-stranded polymeric cation, [.. Ag(tu) (μ-S-tu).. .] ι )(CI0 ) .0.5H O, similar to that observed in CuX/tu (1:3) (X = Cl, Br, I). The remarkable 15:23 nitrate complex (shown to be distinct from the 1:1.5 complex) may be regarded as essentially ionic [Ag (tu) (ONO )] (NO ) (the cation incorporating one O-nitrate ion loosely associated) and comprising one-dimensional polymer strands made up of four-, six-, and eight-membered Ag S rings, cross-linked by the sulfur of one of the tu ligands. The v(CS) and v (CN) bands in the infrared spectra of the complete series of adducts show a monotonic wavenumber decrease and increase, respectively, with decreasing tu content of the adduct, indicating a decrease in the C-S bond strength and a concomitant increase in the C-N bond strength with increasing Ag-S bond strength. The increase in Ag-S bond strength with decreasing tu content is also indicated by an increase in the wavenumbers of the bands assigned to v(AgS) in the 140-200 cm region in the far-IR. These and the structural data for the 1:3 and 15:23 complexes provide the basis for establishing a correlation between v(AgS) and the Ag-S bond length d(AgS) for silver complexes involving the tu ligand. © 2009 American Chemical Society.

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