Synthesis of unusual mixed ligand tellurium(IV) dithiocarbamates with perchlorate. Crystal and molecular structure of perchloratotris(diethyldithiocarbamato)tellurium(IV)

Main Group Dithiocarbamate Complexes

“…Formal substitution of one of the dithiocarbamates in [Te(S 2 CNR 2 ) 4 ] by a uninegative ligand gives seven coordinate Te(IV) complexes of general formulas [TeR(S 2 CNR 2 ) 3 ] and [TeX(S 2 CNR 2 ) 3 ] (R ¼ aryl; X ¼ halide or pseudohalide) (293,304,309,312,319,323,(333)(334)(335)(336)(337)(338)(339)(340)(341)(342). In all cases the geometry at Te is distorted pentagonal bipyramidal, with the uninegative ligand (R or X) axial and one dithiocarbamate ligand spanning axial and equatorial positions.…”

“…Tellurium dioxide reacts with sodium dithiocarbamate salts in the presence or perchloric acid to yield the perchlorate complexes [Te(S 2 CNR 2 ) 3 (ClO 4 )] or [Te 3 (S 2 CNR 2 ) 9 (ClO 4 )(OH) 2 ], depending on the reaction conditions (319). The X-ray molecular structure of [Te(S 2 CNR 2 ) 3 (ClO 4 )] reveals that the perchlorate ligand is weakly bound to the metal center via two oxygen atoms (TeÀ ÀO ¼ 2.87 and 3.12 A ˚).…”