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The title compounds, [1,2‐bis(isopropylsulfanyl)ethane‐2κ2 S,S′]octachlorido‐1κ5 Cl,2κ3 Cl‐μ‐oxido‐ditantalum(V), [Ta2Cl8O(C8H18S2)], (I), and μ‐dimethyldiselane‐κ2 Se:Se′‐μ‐oxido‐bis[tetrachloridotantalum(V)], [Ta2Cl8O(C2H6Se2)], (II), contain six‐coordinate TaV centres linked by a nonlinear oxide bridge. Compound (I) contains one TaV centre bonded to a chelating dithioether and three terminal chloride ligands, with the second TaV centre bonded to five terminal chloride ligands. In (II), two tetrachloridotantalum(V) residues are bridged by the diselenide, giving a puckered five‐membered Ta/O/Ta/Se/Se ring. The Ta—O distances in the bridges are short in both compounds, indicating that significant multiple‐bond character is retained despite the deviation from linearity, and the bond lengths reveal a clear trans influence order of O > Cl > S > Se on the hard TaV centre. The structures are compared with the [Ta2Cl10O]2− anion, which contains a linear oxide bridge.
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Document Type: Research Article

Affiliations: School of Chemistry, University of Southampton, Southampton SO17 1BJ, England

Publication date: July 15, 2011

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