Induced internal electron transfer reactivity of tetrathioperrhenate(VII): Synthesis of the interconvertible dimers Re sub 2 (. mu. -S) sub 2 (S sub 2 CNR sub 2 ) sub 4 and (Re sub 2 (. mu. -SS sub 2 CNR sub 2 ) sub 2 (S sub 2 CNR sub 2 ) sub 3 )(O sub 3 SCF sub 3 ) (R = Me, i-Bu)
- Exxon Research and Engineering Co., Annandale, NJ (USA)
Rhenium sulfides, e.g., ReS{sub 2} and Re{sub 2}S{sub 7}, have long been recognized for their hydrogenation and dehydrogenation reactivity. Periodic trends in catalytic hydrodesulfurization (HDS) reveal rhenium sulfur systems to have high activity. However, discrete, soluble rhenium sulfur species have not received as much attention as have group VI sulfide systems. The tetrathiometalate anions of V, Mo, and W (VS{sub 4}{sup 3{minus}}; MoS{sub 4}{sup 2{minus}}; WS{sub 4}{sup 2{minus}}), which possess fully oxidized (d{sup 0}) metal centers and fully reduced (S{sup 2{minus}}) sulfide ligands, undergo internal redox upon reacting with external oxidants. In these reactions bound sulfide ions (S{sup 2{minus}}) serve as the reductant forming disulfide (S{sub 2}{sup 2{minus}}) concomitant with reduction of the metal center. Conspicuously, ReS{sub 4}{sup {minus}} is the only soluble tetrathiometalate whose chemistry in this regard has not been explored. Here the authors report that tetraalkylthiuram disulfide, acting as an oxidant, induces a dramatic and unprecedented 3e{sup {minus}} reduction of the Re-(VII) center of ReS{sub 4}{sup {minus}}.
- OSTI ID:
- 6518939
- Journal Information:
- Journal of the American Chemical Society; (USA), Vol. 112:17; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHENIUM SULFIDES
SYNTHESIS
DATA ANALYSIS
DIMERS
ELECTRON TRANSFER
MEASURING METHODS
REACTIVITY
CHALCOGENIDES
REFRACTORY METAL COMPOUNDS
RHENIUM COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties