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Fourier transform Raman spectroscopic study of pressure‐induced ligand bond activation in a molybdenum–sulfur cluster
Author(s) -
Butler Ian S.,
Hofstätter Michael,
Müller Achim
Publication year - 2002
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.845
Subject(s) - raman spectroscopy , chemistry , molybdenum , diamond anvil cell , sulfur , ion , crystallography , fourier transform infrared spectroscopy , cluster (spacecraft) , ligand (biochemistry) , fourier transform , nucleophile , analytical chemistry (journal) , high pressure , inorganic chemistry , stereochemistry , organic chemistry , catalysis , mathematical analysis , biochemistry , receptor , physics , mathematics , engineering physics , quantum mechanics , computer science , optics , programming language , engineering
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.