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Trinuclear Tungsten Halide Clusters
Book chapter

Trinuclear Tungsten Halide Clusters

John H Thurston, Vladimir Kolesnichenko, Louis Messerle, Susan E Latturner and William Ainsworth
Inorganic Syntheses: Volume 36, pp.24-29
John Wiley & Sons, Inc
05/02/2014
DOI: 10.1002/9781118744994.ch05

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Abstract

Triangular tritungsten compounds with one or two face‐bridging chalcogenides are well known. Mild main group metal reductants such as mercury, bismuth, antimony, gallium, and Ga + GaCl 4 − are highly effective solid‐state reductants for reducing WCl 6 , MoCl 5 , and TaX 5 (XCl, Br) at considerably lower temperatures than those used in traditional syntheses of group 5 and 6 metal cluster halides. This chapter talks about the preparation of a monocapped, eight‐electron binary tungsten chloride (W 3 Cl 10 ), and the perchlorotritungstates, trisodium tridecachlorotritungstate (Na 3 [W 3 (μ 3 ‐Cl) (μ‐Cl) 3 Cl 9 ]) and tris(benzyltributylammonium) tridecachlorotritungstate ([N(CH 2 Ph)Bu 3 ] 3 [W 3 (μ 3 ‐Cl)(μ‐Cl) 3 Cl 9 ]). The latter trianionic clusters can be oxidized in solution to salts of the seven‐electron isostructural dianion, [N(CH 2 Ph)Bu 3 ] 2 [W 3 (μ 3 ‐Cl)(μ‐Cl) 3 Cl 9 ]. These perchlorotritungsten clusters constitute new synthons, readily accessed from WCl 6 , for the development of tritungsten chemistry. They have potential use in the synthesis of heterometallacubanes and higher nuclearity clusters.
trinuclear tungsten halide clusters tris(benzyltributylammonium) tridecachlorotritungstate trisodium tridecachlorotritungstate tritungsten decachloride

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