Reaktioneil mit N,N-Bis(trimethylstannyl)trifluormethansulfonamid und die Röntgenstrukturanalyse eines zwölfgliedrigen Schwefel-Stickstoff-Ringes / Reactions with N,N-Bis(trimethylstannyl)trifluoromethanesulfonamide and the X-ray Structure of a Twelve-Membered Sulfur-Nitrogen-Ring

The title compound N,N-bis(trimethylstannyl)trifluoromethanesulfonamide (1) reacts with S₂Cl₂, SOCl₂ and SO₂Cl₂ in a molar ratio 2:1 to yield the compounds S₂Cl₂ a twelve-membered ring 6. These are the largest neutral sulfur-nitrogen rings of coordination number two at the sulfur atoms known to date. 3 reacts with SOCI2 under migration of a methyl group from the tin to a sulfur atom to yield CF₃SO₂(R₃Sn)NS(CH₃)NSO₂CF₃ (7).

2,2,4,4-Tetramethyl-1,3-bis(trifluormethylsulfonyl)cyclodisilazan and 7 are formed by the reaction of 3 with R₂SiCl₂- The analogous four-membered germanium compound 8 is obtained from 1 and R₂GeCl₂. While the pyrolysis of 1 yields only the six-membered cyclotristannazan 9, the six-membered germanium analog is only formed in minor amounts. By treating 9 with R₃SiCl the ring is decomposed to give 10. A six-membered ring is formed from the reaction of 1 with ClR₂SiOSiR₂Cl 11. The structure of 6 is discussed in detail. 6 crystallizes in the monoclinic space group C2/c with a = 24.408(5), b = 7.377(2), c = 16.715(3) Å, β = 117.16(3)° and Z = 4. It has a chair conformation which is different from the isoelectronic S₁₂-structure.