Adducts of Lewis acidic stibanes with phosphane chalcogenides

Starting from ClSbR F 2 (R F = C 2 F 5 , 3,5-(CF 3 ) 2 C 6 H 3 ) and H(E)P( t Bu) 2 (E = O, S), we prepared the oxy- and sulphanediyl-bridged adducts R F 2 Sb(Cl)-E-(H)P( t Bu) 2 , which are stable against the elimination of HCl. The different electron-withdrawing substituents and chalcogen bridging units influence the size of the Sb-E-P angle. ClSb(C 2 F 5 ) 2 and n Bu 3 SnH react to give HSb(C 2 F 5 ) 2 , which seems to interact weakly with H(O)P( t Bu) 2 in solution as observed via NMR. All products were characterised by NMR spectroscopy and all the stable ones were additionally characterised by X-ray diffraction and elemental analyses. The Sb-E-P-bridged adducts of (F 5 C 2 ) 2 SbCl and (3,5-(CF 3 ) 2 C 6 H 3 ) 2 SbCl with H(E)P( t Bu) 2 (E = O, S) show different bridging angles depending on substitution and bridging chalcogen atom. Starting from SbCl 3 , we also synthesised the volatile (F 5 C 2 ) 2 SbH.