Sulfonic acids RSO2OH and their metal salts MO3SR are versatile catalysts in large-scale industrial cyclization and polymerization processes. Isoelectronic replacement of the oxygen atoms by NR imido groups gives triimidosulfonic acid and triimidosulfonates. The salts form nonaggregated soluble molecules rather than infinite solid-state lattices such as their oxo analogues. In this paper, we present the synthesis and structure of the basic starting material MeS(N'BU)(3)H (1), the metal complexes [Me2Al(N'Bu)(3)SMe] (2) and [Zn{(N'BU)(3)SMe}(2)] (3), and the mixed metal adduct [(thf)Li{(N'BU)(3)SMe}.ZnMe2] (4). The chelating coordination, rather than the tripodal coordination, cannot be attributed to steric effects of the S-bonded methyl group, as the less demanding Ph-C=C-alkynyl substituent at sulfur in [(thf)(2)Li{(N'Bu)(3)SCCPh}] (5) causes the same conformation. S-N bond shortening to the pendant imido group has to be attributed to closed-shell electrostatic attraction rather than to S-N double bonding by valence expansion at the central sulfur atom. Coordination to an additional N --> Zn dative bond in 4 widens the bond length to values normally interpreted as S-N single bonds. We take this fact as experimental evidence that S-N bonding is predominantly governed by electrostatic interaction rather than by valence expansion employing d-orbitals. This was predicted by theoreticians more than a decade ago.