
%0 Journal Article
%A Tiekink, Edward R. T. 
%A Eagle, Aston A. 
%A Young, Charles G. 
%T Facets of Induced Internal Redox Involving WS<emph type="8">4</emph><emph type="7">2&#8211;</emph> and WSe<emph type="8">4</emph><emph type="7">2&#8211;</emph>: Synthesis and X-Ray Crystal Structures of <emph type="2">syn</emph>-W<emph type="8">2</emph>S<emph type="8">2</emph>(&#956;-S)<emph type="8">2</emph>(S<emph type="8">2</emph>PPh<emph type="8">2</emph>)<emph type="8">2</emph> and WO(Se<emph type="8">2</emph>)(S<emph type="8">2</emph>CNEt<emph type="8">2</emph>)<emph type="8">2</emph>
%J Australian Journal of Chemistry
%D 2000/12/22
%V 53
%N 9
%P 779-784
%K Redox; tungsten; tetraseleno; tetrathio; sulfur; dithiophosphinate complex; oxo(diselenido) complex; X-ray crystal structure.
%R https://doi.org/10.1071/CH00104
%U https://www.publish.csiro.au/paper/CH00104 
%X Reaction of (NEt4)2&#91;WS4&#93; and &#91;S2PPh2&#93;2 in acetonitrile results in the formation of diamagnetic, orange syn-W2S2(&#181;-S) 2(S2PPh2)2 by an induced internal redox process. Crystals of the toluene solvate W2S2(&#181;-S) 2(S2PPh2)2 . C7H8 are triclinic and belong to space group P1&#8211; with a 13.845(5), b 16.536(7), c 8.387(2) &#197;, &#945; 99.75(3), &#946; 95.51(3), &#947; 83.08(3)&#x02DA;, and Z 2. Refinement of 5445 data converged at R 0.038 and Rw 0.038. The complex possesses a syn-&#91;W V 2S2(&#181;-S)2&#93;2+ core with a W&#8211;W bond of 2.8161(5) &#197; and two terminal W=S bonds of 2.097(3) and 2.096(3) &#197;. The W-(&#181;-S) bond distances are in the range 2.310(2)&#8211;2.315(2) &#197;. Each of the five-coordinate, square-pyramidal tungsten atoms is further coordinated by a bidentate dithiophosphinate ligand with W&#8211;S bond distances ranging from 2.464(2) to 2.481(2) &#197;. Extended reaction of (NH4)2&#91;WSe4&#93; and &#91;S2CNEt2&#93;2 in acetonitrile produces green WS(Se2)(S2CNEt2)2 and red WO(Se2)(S2CNEt2)2 in 40% and 15% yields, respectively. Crystals of WO(Se2)(S2CNEt2)2 are monoclinic and belong to space group P21/n with a 9.609(6), b 15.053(7), c 13.120(9) &#197;, &#946; 100.08(4)&#x02DA;, and Z 4. Refinement of 2473 data converged at R 0.039 and Rw 0.039. The seven-coordinate, pentagonal bipyramidal complex features C1 symmetry, an axial oxo ligand (W=O 1.705(6) &#197;), an equatorial, side-on bonded diselenido ligand (W&#8211;Se(1) 2.509(1), W&#8211;Se(2) 2.547(1) &#197;, Se(1)&#8211;Se(2) 2.306(2) &#197;) and two bidentate dithiocarbamate ligands. 
