Skeletal scrambling of sulphur diimide radical anions

Abstract

. 6 9 , 9 4 (1991). In the presence of a catalytic quantity of alkali metal mixtures of sulphur diimides RNSNR and R'NSNR' (R, R' = Ph, 4-C6H4Me, 4-C6H40Me, SiMe,, SPh) undergo a rapid scrambling of the R and R' groups. When R and R' are significantly different (e.g., R = Ph, R' = SiMe, or SPh) the equilibrium is shifted to favour the unsymmetrical sulphur dimmide (R 4= R'); the procedure thus represents an effective method for preparing such derivatives. A mechanism involving the centrosymmetric association and rearrangement of two sulphur diimide radical anions is suggested for the observed ligand scrambling. The synthesis and X-ray structure determination of the mixed diimide (4-N02C6H4)SNSN(4-C6H40Me) is reported.The crystals are monoclinic, space gr0upP2~ln; the molecules stack as plates along the a axis in a head-to-head fashion, producing an interplanar spacing between consecutive SzNz units of 3.42 1 A.Key words: sulphur diimide radical anions, skeletal rearrangements, (4-C6H4N0,)SNSN(4-C6H40Me), X-ray structure.KETUT BESTARI, RICHARD T. OAKLEY et A . WALLACE CORDES. Can. J. Chem. 69, 94 (1991). En prksence d'une quantitC catalytique d'un mCtal alcalin, des mklanges des diimides du soufre RSNSNR at R'NSNR' (R, R' = Ph, 4-C6H4Me, 4-C6H40Me, SiMe, et SPh) subissent un brouillage rapide des groupements R et R'. Lorsque R et R' sont des groupements assez diffkrents (par exemple, R = Ph et R' = SiMe, ou SPh), I'Cquilibre est dCplack vers le diimide de soufre non-symktrique (R 4= R'); cette proc6dure reprksente donc une m6thode efficace pour prkparer de tels dkrivCs. Pour expliquer le brouillage observC des ligands, on propose un mkcanisme impliquant une association centrosymetrique et une transposition de deux anions radicaux des diimides du soufre. On rapporte la synthkse et la dktermination de structure (par diffraction des rayons-X) du dimrnide mixte (4-NOrC6H4)SNSN(4-C6H40Me). Les cristaux sont rnonocliniques, groupe d'espace P2,/n; les molCcules s'empilent le long de l'axe a sous la forme de plaquettes dans lesquelles elles sont arrangkes d'une fason t&te-g-t&te provoquant un espacement de 3,421 A entre les plans de deux unit6 successives de S2N2.

Structures and EPR spectra of binary sulfur–nitrogen radicals from DFT calculations

“…which could provide a facile pathway for the conversion of S2N2 to S4N4 [6]. A similar mechanism was proposed to explain the scrambling of sulfur diimides, RN=S=NR', which occurs rapidly in presence of a catalytic amount of reducing agent [45]. [25].…”

The First Lanthanide Complexes with a Redox‐Active Sulfur Diimide Ligand: Synthesis and Characterization of [LnCp*2(RN=)2S], Ln=Sm, Eu, Yb; R=SiMe3

“…[11] Importantly,t hese RAs were never isolated;f urthermore, the chemistry of [(RN=) 2 S] À C is practically unknown except for their purported involvement in interesting skeletal scrambling reactions that enablet he synthesis of nonsymmetrical derivatives RÀN=S=NÀR' (R, R' = Ar) from amixture of corresponding symmetrical ones. [12] The redox activity of sulfur diimides makes them potential non-innocent ligands. [13] Although the coordination chemistry of (RN=) 2 Si sr ather extensive, [10a, 14] the possibility of spontaneous metal-to-ligand electron transfer has apparently never been considered.…”

SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF THE ASYMMETRIC DITHIADIAZENE BrC6F4NSNSC6H4NO2

“…Conversely, a single report indicated that condensation reactions between sulfenyl chlorides (RSCl) and trimethylsilyl protected sulfur diimides can be used to produce asymmetric dithiadiazenes. 5 The methodology detailed in Scheme 1 represents a clean stepwise synthesis of the target compound, BrC 6 F 4 NSNSC 6 H 4 NO 2 (1) in reasonable yield, and has been applied to prepare several other similar compounds in this laboratory. …”