Novel Asymmetrical Dianionic Polyimido-Sulfur(IV)-Ylides

Carola Selinka 1  and Dietmar Stalke 1
  • 1 Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, D-97074 Würzburg

Sulfurdiimides RN=S=NR react in donating solvents with two equivalents of lithiumalkyls to give the dimeric C,N-dilithium-methylenediimidosulfite solvent adducts [(Et2O)Li2{H2CS-(NSiMe3)(NtBu)}]2 (1) and [(thf)Li2{H8C4S(NtBu)2}]2 (2). Firstly, addition of a lithiumalkyl to sulfurdiimide gives the diimidosulfinates [RS(NR')2]- (1: R = Me, R′ = tBu, SiMe3; 2: R = nBu; R′ = tBu) while in a second step the α-carbon atom in R is metalated with one equivalent of lithiumalkyl to give the asymmetric S-ylides. The reaction of 3-bromothiophene with one equivalent of nBuLi and one of sulfurdiimide tBuN=S=NtBu resulted in the dilithium-3-thiophenylenediimidosulfite [(thf)Li2{(SC4H2)S(NtBu)2}]2 (3). It can be regarded

as the first example of a dianionic S(IV)-β-ylide. This class of compounds can be rationalised as sulfite analogues, where two oxygen atoms are isoelectronically replaced by a NR group each and the remaining oxygen atom is replaced by a CR2 group. The rich coordination chemistry of the triimidosulfites is extended by the introduction of a hard carbanionic centre.

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Zeitschrift für Naturforschung B is an international scientific journal which publishes original papers, microreviews, and letters from all areas of inorganic chemistry, solid state chemistry, coordination chemistry, molecular chemistry, and organic chemistry.