Polysulfonylamines .66. In search of long Si(sp(3))-N(sp(3)) bonds: Synthesis of N,N-disulfonylated silylamines and solid-state structure of (4-Cl-C6H4SO2)(2)N-SiMe(3)

Twelve new N,N-di(organosulfonyl) silylamines (R(1)SO(2))(2)N-SiR(2)R(3)R(4), where R(n) = alkyl or aryl, were obtained as moisture-sensitive solids or liquids by treating the silver salts (R(1)SO(2))(2)NAg with chlorosilanes ClSiR(2)R(3)R(4) in MeCN solution. Some of the compounds appear to establish N,O-silylotropy equilibria in solution (NMR evidence). The crystallographic data for (4-Cl-C6H4SO2)(2)N-SiMe(3) are (at -75 degrees C): triclinic, space group <P(1)over bar>, a = 659.2(3), b = 1134.5(5), c = 1334.3(6) pm, alpha = 96.52(3), beta = 103.35(3), gamma = 93.32(3)degrees, V = 0.9610(7) nm(3), Z = 2. The Me(3)Si group is attached to the nitrogen atom through an unusually long Si-N bond (184.3 pm). Concomitantly, the SN bonds are relatively short (166.9 and 168.1 pm). The bond angles of the trigonal-planar SINS, unit are distorted by an intramolecular 1,4-interaction between silicon and a sulfonyl oxygen atom (Si ... O 286.3 pm, Si-N-S 117.2 and 123.8, S-N-S 118.6 degrees, sum of bond angles at nitrogen 359.6 degrees).