68:
246:
234:
17:
47:. Two isomers have been studied: the 1,2‑dithia-3,5‑diazoles, in which the sulfur atoms are bonded to each other across the ring from the carbon atom, and the 1,3‑dithia-2,5‑diazoles, in which nitrogen and sulfur atoms alternate around the ring. In both cases, the neutral species are
428:
Bryan, C. D.; Cordes, A. W.; Fleming, R. M.; George, N. A.; Glarum, S. H.; Haddon, R. C.; MacKinnon, C. D.; Oakley, R. T.; Palstra, T. T. M.; Perel, A. S. (1995). "Charge
Transfer Salts of Benzene-Bridged 1,2,3,5-Dithiadiazolyl Diradicals. Preparation, Structures, and Transport Properties of 1,3- and
404:
MacLean, Gregory K.; Passmore, Jack; Rao, M. N. Sudheedra; Schriver, Melbourne J.; White, Peter S.; Bethell, Donald; Pilkington, Roger S.; Sutcliffe, Leslie H. (1985). "Preparation of 1,3,2-dithiazolium hexafluoroarsenate(V), preparation and crystal structures of 5-methyl-1,3,2,4-dithiadiazolium and
376:
Cordes, A. W.; Bryan, C. D.; Davis, W. M.; De Laat, R. H.; Glarum, S. H.; Goddard, J. D.; Haddon, R. C.; Hicks, R. G.; Kennepohl, D. K. (1993). "Prototypal 1,2,3,5-dithia- and -diselenadiazolyl (E = sulfur, selenium): Molecular and electronic structures of the radicals and their dimers, by theory
84:
The structures of both the 1,2-dithia-3,5-diazolium cations and the neutral 1,2-dithia-3,5-diazoles are fairly similar. These are planar five-membered rings. With one electron in a π*-level, the neutral ring has longer bonds vs the cation. The elongation is a few percent. For example, the S–S
189:
substitutes cheaply for thiazyl chloride, but product yields are small. Alternatively, sulfur dichloride reacts with amidines to give dithiadiazolium chlorides, albeit with sensitivity to reaction conditions.
512:
Lau, Hiu Fung; Ang, Pearly Chwee Ying; Ng, Victor Wee Lin; Kuan, Seah Ling; Goh, Lai Yoong; Borisov, Alexey S.; Hazendonk, Paul; Roemmele, Tracey L.; Boeré, René T.; Webster, Richard D. (2008). "Coupling of
51:
that are of interest as examples of paramagnetic heterocycles. They have also attracted interest because of the tendency of the neutral species to form
20:
Part of the structure of 1,2‑dithia-3,5‑diazole highlighting the stacking motif common for these compounds. Color code: yellow = S, blue = N, gray = C.
321:
1,3-Dithia-2,5-diazolium salts, which lack the S–S bond, are less common than the 1,2,3,5 isomer. The neutral 1,3-dithia-2,5-diazoles are even rarer.
572:
325:
485:
Rawson, Jeremy M.; Banister, Arthur J.; Lavender, Ian (1995). "The
Chemistry of Dithiadiazolylium and Dithiadiazolyl Rings".
353:
The singly-reduced dithiazole radical is unstable, isomerizing to 1,2‑dithia-3,5‑diazole or forming uncharacterized
562:
250:
567:
557:
109:
333:
517:
and
Heterocyclic Dithiadiazolyl Radicals. Synthetic, X-ray Diffraction, Dynamic NMR, EPR, CV, and DFT Studies".
405:
4-methyl-1,3,2-dithiazolium hexafluoroarsenate(V) and the reduction of these salts to stable free radicals".
149:
56:
52:
33:
94:
48:
446:
283:
534:
182:
178:
526:
494:
438:
410:
386:
310:
287:
291:
306:
498:
67:
551:
98:
71:
Bond distances and bond angles of 1,3- and 1,2-dithiadiazolium cations. Distances in
450:
245:
186:
105:
342:
The electrophilicity of dithiadiazolium salts is indicated by their tendency to
198:
108:) spin-paired dimers via weak S---S interactions. The neutral species' slight
298:
233:
120:
116:
16:
115:
For the 1,2-dithia-3,5-diazolium salts, their bright colors vary with the R
72:
25:
538:
414:
442:
390:
131:
The traditional entry to dithiadiazoles is reduction the mono-cation RCN
329:
302:
145:
530:
257:
Halogens typically reoxidize dithiadiazoles to dithiazolium cations:
194:
101:
354:
347:
244:
232:
66:
15:
343:
193:
The dithidiazolium cations are reduced by treatment with
63:
1,2-Dithia-3,5-diazoles and their oxidized derivatives
407:
Journal of the
Chemical Society, Dalton Transactions
324:The synthesis of these salts involves addition of
282:Dithiadiazoles react with low-valent metal ion by
104:. Dithiadiazole radicals equilibrate with their (
144:. These cations are obtained by the addition of
339:The sulfur atoms bear a slight positive charge.
225:A variety of reducing agents can be employed.
112:places a positive charge on the sulfur atoms.
8:
480:
431:Journal of the American Chemical Society
379:Journal of the American Chemical Society
371:
369:
177:For large-scale syntheses, a mixture of
170:
166:
162:
158:
93:is 207 vs 201 pm in the cation. Melting
43:
39:
478:
476:
474:
472:
470:
468:
466:
464:
462:
460:
365:
350:through a poorly-understood mechanism.
286:of the S–S bonds. The products feature
332:. The conversion is an example of a
7:
241:-bis(1,2,3,5-dithiadiazolyl) (BDTDA)
249:BDTDA honeycomb lattice on copper,
326:dithionitronium hexafluoroarsenate
14:
288:bidentate dithiolate-like ligands
290:, each sulfur functioning as a
1:
499:10.1016/S0065-2725(08)60422-5
157:2 RCN + 4 NSCl → 2 [RCN
85:distance in the neutral HCN
589:
97:these dimers to produce a
573:Sulfur–nitrogen compounds
334:1,3-Dipolar cycloaddition
205:2 → 2 RCN
346:. They hydrolyze to an
317:1,3-Dithia-2,5-diazoles
305:-hydrochloride salts,
297:Dithiadiazolium salts
254:
242:
76:
53:linear chain compounds
34:heterocyclic compounds
21:
563:Nitrogen heterocycles
248:
236:
70:
57:molecular electronics
19:
487:Adv. Heterocyc. Chem
415:10.1039/dt9850001405
568:Five-membered rings
558:Sulfur heterocycles
519:Inorganic Chemistry
443:10.1021/ja00131a009
429:1,4- (X = I, Br)".
391:10.1021/ja00069a022
187:chlorine atmosphere
284:oxidative addition
255:
243:
77:
22:
531:10.1021/ic702128f
437:(26): 6880–6888.
385:(16): 7232–7239.
377:and experiment".
183:sulfur dichloride
179:ammonium chloride
36:with the formula
580:
543:
542:
509:
503:
502:
482:
455:
454:
425:
419:
418:
401:
395:
394:
373:
311:elemental sulfur
273:
272:
240:
217:
216:
173:
150:thiazyl chloride
143:
142:
46:
32:are a family of
588:
587:
583:
582:
581:
579:
578:
577:
548:
547:
546:
516:
511:
510:
506:
484:
483:
458:
427:
426:
422:
403:
402:
398:
375:
374:
367:
363:
319:
292:bridging ligand
277:
271:
268:
267:
266:
264:
238:
237:Molecule of 4,4
231:
221:
215:
212:
211:
210:
208:
172:
168:
164:
160:
156:
141:
138:
137:
136:
134:
129:
92:
88:
82:
65:
45:
41:
37:
12:
11:
5:
586:
584:
576:
575:
570:
565:
560:
550:
549:
545:
544:
525:(2): 632–644.
514:
504:
456:
420:
396:
364:
362:
359:
344:polymerize THF
318:
315:
307:sulfur dioxide
280:
279:
275:
269:
262:
230:
227:
223:
222:
219:
213:
206:
175:
174:
139:
132:
128:
125:
90:
86:
81:
78:
64:
61:
30:dithiadiazoles
13:
10:
9:
6:
4:
3:
2:
585:
574:
571:
569:
566:
564:
561:
559:
556:
555:
553:
540:
536:
532:
528:
524:
520:
508:
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500:
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469:
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452:
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436:
432:
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408:
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372:
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308:
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295:
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204:
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200:
196:
191:
188:
184:
180:
155:
154:
153:
151:
147:
126:
124:
122:
118:
113:
111:
110:dipole moment
107:
103:
100:
96:
79:
74:
69:
62:
60:
58:
55:, a theme in
54:
50:
35:
31:
27:
18:
522:
518:
507:
490:
486:
434:
430:
423:
406:
399:
382:
378:
352:
341:
338:
323:
320:
296:
281:
256:
224:
192:
176:
130:
114:
99:paramagnetic
83:
29:
23:
409:(7): 1405.
199:thiocyanate
106:diamagnetic
552:Categories
361:References
357:polymers.
278: → 2X
261:2 RCN
121:counterion
117:side chain
80:Structures
73:picometers
299:hydrolyze
274: + X
229:Reactions
218: + I
127:Synthesis
26:chemistry
539:18161967
513:CpCr(CO)
451:96841129
328:() to a
185:under a
165:]Cl + Cl
146:nitriles
119:and the
49:radicals
330:nitrile
303:amidine
537:
449:
309:, and
195:iodide
102:liquid
95:cracks
447:S2CID
355:brown
348:amide
253:image
535:PMID
197:and
181:and
148:and
527:doi
495:doi
439:doi
435:117
411:doi
387:doi
383:115
301:to
251:STM
169:+ N
38:RCN
24:In
554::
533:.
523:47
521:.
493:.
491:62
489:.
459:^
445:.
433:.
381:.
368:^
336:.
313:.
294:.
201::
152::
123:.
59:.
28:,
541:.
529::
515:3
501:.
497::
453:.
441::
417:.
413::
393:.
389::
276:2
270:2
265:S
263:2
239:′
220:2
214:2
209:S
207:2
171:2
167:2
163:2
161:S
159:2
140:2
135:S
133:2
91:2
89:S
87:2
75:.
44:2
42:S
40:2
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