Preparation of Iodotris(dithiocarbamato)tellurium(Iv) Complexes, and Crystal Structure of Iodotris(piperidine-1-carbodithioato)tellurium(IV)

Abstract

Mixed iodotris ( dithiocarbamato )tellurium(IV) complexes TeL3I (where L- = R1R2NCS2-) have been synthesized with the use of the oxidative replacement reaction via the interaction of TeL4 with iodine. Thus, complexes with R1 = R2 = methyl, ethyl, isopropyl, propyl, and with R1R2N= piperidinyl * have been prepared. A single-crystal structure analysis of one of these, iodotris ( piperidine dithiocarbamato )tellurium, is also reported. In the structure the tellurium atom exists in a distorted pentagonal-bipyramidal environment with the iodine atom and one sulfur atom occupying axial positions. The axial Te-S bond of 2.555(2) � is shorter than the remaining Te-S bonds in the complex [range 2.671(2)-2.722(2) � ]. Crystals are monoclinic, space group P2I/n with unit cell parameters a 9.891(2), b 18.889(2), c 14.762(2) �, β 98.85(2) and Z 4. The structure was refined to final R 0.035 and RW 0.052 for 3283 reflections with 1≥ 1.25 σI).

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.…”