FORMATION AND IDENTIFICATION OF BIS[BIS(TRIMETHYLSILYL)AMINO]TRICHALCOGENIDES AND TETRACHALCOGENIDES

The reaction of (Me(3)Si)(2)NLi with SCl2 and elemental sulfur or with Se2Cl2 and elemental selenium leads to the formation of mixtures of bis[bis(trimethylsilyl)amino]sulfides and selenides [(Me(3)Si)(2)N](2)E(x) (E = S or Se; x = 1-4). The reaction products were identified by mass spectroscopy as well as by Se-77 and C-13 NMR spectroscopy. The reaction of (Me(3)Si)(2)NH with S2Cl2 produces [(Me(3)Si)2N]S-2(3) as the main product with only traces of other aminosulfides. [(Me(3)Si)2N]S-2(3) was purified by distillation under reduced pressure and identified by elemental analysis, mass spectroscopy, and by H-1, C-13, and N-14 NMR spectroscopy The successful cyclocondensation reaction of [(Me(3)Si)2N]S-2(3) With SCl2 and SO2Cl2 produces S4N2 in 72% yield and provides further verification of the identity of bis[bis(trimethylsilyl)amino]trisulfide. While the analogous reaction of (Me(3)Si)(2)NH with Se2Cl2 also leads to the formation [(Me(3)Si)(2)N]Se-2(2) and [(Me(3)Si)2N]Se-2(4) in significant amounts (17 and 35 mol %, respectively). Attempts to purify the mixture by distillation under reduced pressure resulted only in the formation of a 83:17 mixture of [(Me(3)Si)2N]Se-2(2) and [(Me(3)Si)2N]Se-2(3).