Fourier transform Raman spectroscopic study of pressure-induced ligand bond activation in a molybdenum–sulfur cluster
✍ Scribed by Ian S. Butler; Michael Hofstätter; Achim Müller
- Publisher
- John Wiley and Sons
- Year
- 2002
- Tongue
- English
- Weight
- 146 KB
- Volume
- 33
- Category
- Article
- ISSN
- 0377-0486
- DOI
- 10.1002/jrs.845
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✦ Synopsis
Abstract
Fourier transform Raman spectra of the prototype, triangular, transition metal–sulfur cluster anion [Mo~3~(S~2~)~6~S]^2−^ were recorded at pressures up to 60 kbar with the aid of a diamond‐anvil cell (DAC). The pressure dependences (∂ν/∂p) of the Raman bands indicate a structural change at around 10–15 kbar. The SS stretching mode for the bridging disulfide ligands exhibits a slightly negative ∂ν/∂p value (−0.08), suggesting that SS bonds are weakened, i.e. activated, at high pressures. This pressure‐induced activity parallels the observed nucleophilic substitution reactivity of the S~2~ groups in this molybdenum cluster anion. In view of this, a preliminary investigation of the reaction between [Mo~3~(S~2~)~6~S]^2−^ and CN^−^ was undertaken in the solid state in the DAC under high pressure. Copyright © 2002 John Wiley & Sons, Ltd.