title: Arylthiazylamides: syntheses, structures, and bonding properties.
abstract: Air-sensitive, thermally unstable tris(dimethylamino)sulfonium (TAS) salts (3) of the title anions [ArNSN]- have been prepared from corresponding sulfurdiimides Ar-N=S=N-SiMe3 (2) by Si-N bond cleavage with [(Me2N)3S]-[Me3SiF2]- (TASF). They are characterized by low-temperature X-ray crystallography as Z isomers. Because of the very short terminal S-N distance (144.2 (3h)-147.9 (3i)pm) and the relatively long internal S-N distance (158.3 (3i)-160.3 (3c) pm) the [ArNSN]- ions should be regarded as thiazylamides 1b, rare species containing a S triple bond N triple bond. A bonding model is developed and the experimental results are compared with those of restricted Hartree-Fock (RHF), density functional theory (DFT), and Møller-Plesset second-order (MP2) calculations.
authors.affiliation: Institute of Organic Chemistry, Bremen University, Germany.
authors.forename: T
authors.initials: T
authors.lastname: Borrmann
authors.forename: E
authors.initials: E
authors.lastname: Lork
authors.forename: R
authors.initials: R
authors.lastname: Mews
authors.forename: W D
authors.initials: WD
authors.lastname: Stohrer
authors.forename: P G
authors.initials: PG
authors.lastname: Watson
authors.forename: A V
authors.initials: AV
authors.lastname: Zibarev