1,2,3,5-Dithiadiazolyles, a new type of persistent sulfurnitrogencontaining radicals

Novel S–N ring contractions using the 4-phenyl-1,2,3,5-dithiadiazole dimer, the synthesis and X-ray crystal structures of [(PhCN2S2)2Cl][S3N3], [PhCN2S2][S3N3], and [PhCN2S2][S3N2]Cl, and an ab initio molecular-orbital study of the bonding in [PhCN2S2][S3N3]

“…Young Teflon-stemmed greaseless vacuum tap, (3) Pyrex sinter (usually porosity grade 3), and (4) outside diameter, ;-in tubing for coupling to vacuum line using a $in 'Swagelok' union with Teflon ferrules. (b)Sublimation apparatus for mixing the vapours of (SN), and (PhCN,S,),: (1) two-tier sublimation tube, (2) upper tier in shape of an annular groove, containing (SN), crystals at 160 "C, (3) bottom tier, containing (PhCN,S,), crystals at 50 "C, (4) mixing-reaction zone filled with lightly compacted quartz wool (Thermal Syndicate, Ltd., type A), (5) cold-finger, (6) connection to a high vacuum unit, (7) J. Young greaseless ball joint, and (8) transparent resistance furnaces with control thermocouples and silver nitrate respectively.…”

“…Additional material available from the Cambridge Crystallographic Data Centre comprises H-atom co-ordinates, thermal parameters, and remaining bond lengths and angles. (5).-The salt [PhCN2-S2]Cl (1 .OOO g, 3.766 mmol), AgAsF, (1.1 18 g, 3.766 mmol), and a Teflon-coated magnetic stirrer bar were placed in one bulb of a two-bulbed reaction vessel. Sulphur dioxide (10 cm3) was condensed onto the mixture using an acetone-solid C 0 2 bath at -78 "C and the mixture was warmed to room temperature with vigorous stirring.…”

Metal-radical coordination complexes of thiazyl and selenazyl ligands

“…This is, in part, due to valuable and reliable synthetic methodologies that A c c e p t e d M a n u s c r i p t 4 have made it possible to synthesize RDTDA species with a wide range of R substituents ( Fig. 1) [27][28][29][30][31][32][33]. As such, it is not surprising that DTDAs were the first class of thiazyl radical to be investigated with respect to metal coordination (vide infra) as well as the species for which the largest number of metal-thiazyl coordination complexes having been reported to date.…”

The Synthesis and Characterization of Stable Radicals Containing the Thiazyl (SN) Fragment and Their Use as Building Blocks for Advanced Functional Materials

“…Other routes have been reported but tend to be substrate-specific (for example Mews has developed routes to the 4-halogeno-1,2,3,5-dithiadiazolium cations starting from N,Nbis(trimethylsilyl)carbodiimide). 88 Reduction of the dithiadiazolium cations 36 to the radicals 35 can be carried out with metals (sodium, 89 zinc, mercury, potassium, zinc/copper couple 90 ) organic/organometallic reagents (tetramethyl-p-phenylenediamine, triphenylverdazyl, 89 triphenylantimony 91,92 ), or reducing anions (SCN − , I − , Grignard reagents, CN − , N 3 − ). 90 The electronic structure of 1,2,3,5-dithiadiazolyl radicals 35 has been thoroughly probed.…”