Tetrathiomolybdate ion

The tetrathiomolybdate ion [16550-92-0] (Fig. 2b), which has received great attention in the late 20th century, was first reported by BerzeHus in 1838. The simple preparation from molybdate in basic aqueous solution occurs in high yield according to ... 

The red tetrathiomolybdate ion appears to be a principal participant in the biological Cu—Mo antagonism and is reactive toward other transition-metal ions to produce a wide variety of heteronuclear transition-metal sulfide complexes and clusters (13,14). For example, tetrathiomolybdate serves as a bidentate ligand for Co, forming Co(MoSTetrathiomolybdates and their mixed metal complexes are of interest as catalyst precursors for the hydrotreating of petroleum (qv) (15) and the hydroHquefaction of coal (see Coal conversion processes) (16). The intermediate forms MoOS Mo02S 2> MoO S have also been prepared (17). 

Tetrathiafulvalene (TTF), 23 707 electrochromic material, 6 581, 581t polymers of, 23 708-709 Tetrathiomolybdate ion, 17 22-23 Tetravalent lead, 14 783 Tetravalent manganese compounds,... 

Disulfides can be prepared by treatment of alkyl halides with disulfide ions and also indirectly by the reaction of Bunte salts (see 10-41) with acid solutions of iodide, thiocyanate ion, or thiourea, or by pyrolysis or treatment with hydrogen peroxide. Alkyl halides also give disulfides when refluxed with sulfur and NaOH, and with piperidinium tetrathiotungstate or piperidinium tetrathiomolybdate. ... 

The structure consists of a tetrahedral arrangement of sulfur atoms around each molybdenum and copper atom, with each tetrahedron sharing two comers with each of its two neighbors. The ammonium Ions are located in the spaces between the chains. The Mo-S distance is 2.19 A in accord with those found in (NH4)2MoS4193. A structure determination has been carried out also on pipera-zinium tetrathiomolybdate, (C4H12N2)MoS4195. The MoS42 anion is tetrahedral with Mo-S distances 2.18 A, and the piperazinium ion is in the chair form. 

More recently Buckler et al. (210) and Lutz et al. (211) have studied the isotope effect on Mo shielding in molybdate ( 0/ 0) and tetrathiomolybdate ( " S/ S). In the latter case the isotope peak can be observed at the natural abundance of (4-2%) on the species (14%). An isotope effect of 0-25 ppm towards lower frequencies is observed upon exchange of one by The isotope shift induced by (relative to S) in M0S4" was found to be 0 09 ppm to low frequency. This represents a rare case where the shielding isotope effects are known for two isotope pairs and identical molecular geometries since both ions are tetrahedrally coordinated. As a first approximation the isotope effect on the shielding should be proportional to (mi" — ) with mi and m2 representing the mass... 

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