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DOI: 10.1039/A903918J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2877-2883

Sulfur–sulfur bonding in the amorphous sulfides WS3, WS5, and Re2S7 from sulfur K-edge EXAFS studies

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Simon J. Hibble, Richard I. Walton, Mark R. Feaviour and Andrew D. Smith

Abstract

The measurement of extended X-ray absorption fine structure (EXAFS) using energy-selective fluorescence detection in the soft X-ray region has enabled sulfur K-edge EXAFS studies of the amorphous sulfides WS3, WS5 and Re2S7, to be carried out for the first time. Quantitative information about the local environment of sulfur in these highly structurally disordered sulfides has been obtained and is compared with that obtained by previous EXAFS studies at the metal LIII edges. The average oxidation state of sulfur and hence the metals in these amorphous sulfides is derived from S–S co-ordination numbers. Results from the crystalline model compound [NH4]2[W3(µ3-S)(µ-S)3(S4)3(NH3)3] are also presented to give an indication of the reliability of the results. In all the amorphous compounds studied S–S bonds with bond lengths close to 2.0 Å are found. In WS3 each sulfur has on average 0.5 sulfur near neighbours and close to 2 tungsten near neighbours at 2.43 Å. In WS5 each sulfur has on average 1 sulfur near neighbour and ≈1.2 tungsten near neighbours at 2.46 Å, consistent with the material being formulated as WV(S22–)2.5. Amorphous Re2S7 also contains sulfur with an average sulfur co-ordination number of 1 and the compound is thus formulated as Re3.52(S22–)3.5. The S–Re bond distance is found to be 2.32 Å. All the S-M distances found are in excellent agreement with those found from previous metal LIII-edge EXAFS studies. Possible structural models for the amorphous materials are discussed.

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