A series of hitherto unreported solid salts of penta-coordinated cations of the general formula [R 2 SbL 3 ] 3þ , where R ¼ C 6 H 5 , p-ClC 6 H 4 , p-CH 3 C 6 H 4 , p-(CH 3 O)C 6 H 4 ; L ¼ DMSO, Ph 3 AsO, Py-N-oxide, DMF, a-, b-, and g-picoline have been prepared in the presence of tetraphenyland tetrafluoro-borate counterions. The complexes have been formulated and characterized on the basis of elemental analyses, molar conductances, molecular weights, and solid state IR and solution state 1 H NMR spectral 459