L,3-Dithiole-2-thione-4,5-dithiolate dmit

Cassoux P, Valade L, Kobayashi H, Kobayashi A, Clark RA, Underhill AE (1991) Molecular metals and superconductors derived from metal complexes of l,3-dithiol-2-thione-4, 5-dithiolate (dmit). Coord Chem Rev 110 115-160... 

Heterocyclic thiones l,3-dithiole-2-thione-4,5-dithiolate (DMIT). N. Svenstrup and J. Becher, Synthesis, 215 (1995). 

Other complexes of thiocarbonyl compounds related to dmit, such as 1,2-dithiole-3-thione-4,5-dithiolate (dmt, 161)741,744,752, l,3-dithiole-2-thione-4,5-diselenolate (dsit, 162)687,753-758 or l,3-thiaselenole-2-thione-4,5-dithiolate (dmits, 163)699 have been described. 

Organotin 1,2-dithiolate complexes were featured in many studies the ligands used include aliphatic derivatives, e.g. ethane-1,2-dithiolate -SCH2CH2S-(EDT), -SCH2CHMeS-, alkenyl derivatives, e.g. -SCH=CHS-, maleonitriledithiolate (MNT), aryl derivatives, 1,2--SC6H4S (BDT) and toluene-3,4-dithiolate (TDT), as well as heterocyclic derivatives, l,3-dithiane-2-one-4,5-dithiolate (DMIO) and l,3-dithiane-2-thione-4,5-dithiolate (DMIT)191. 

Consequently, we will centre our attention on the main type of acceptors according to their different molecular nature. Thus, we will focus on derivatives of the parent molecules TCNQ, dicyano-p-quinonediimine (DCNQI), other polycyano derivatives, dithiolene metal complexes (l,3-dithioIe-2-thione-4,5-dithiolate, dmit) and some interesting cases in the emerging chemistry of fullerene [13] derivatives as shown in Figure 1.1. 

The structure of [Mo3S4(dmit)3] (dmit=l,3-dithiole-2-thione-4,5-dithiolate) represents one of the rare examples of M3S4 clusters where each metal atom appears as pentacoordinate instead of its more common type-I structure octahedral environment [39]. Complexes [M3Q4(dmit)3] (M = Mo, W Q = S, Se) degrade in air with an almost quantitative yield and afford a series of M(V) dimers of formula [M202(//-Q)2(dmit)2] where the oxygen atoms are in a syn configuration. 

M(dmit)2 complexes (dmit = C3S52- = l,3-dithiole-2-thione-4,5-dithio-late) constitute one of the most important subclasses. The most studied metal complexes are those of group 10 (Ni, Pd, Pt), which possess a square-planar geometry see for instance the molecular structure of the monoanion [Ni(dmit)2], Figure 42.73... 

K[Os(N)(CH2SiMe3)2(bdt)] and (NBu4)[Os(N)(CH2SiMe3)2(dmit)] (dmit= l,3-dithiol-2-thione-4,5-dithiolate) have also been reported. " ... 

A very important ion related to thiocarbonyl compounds is the l,3-dithiole-2-thione-4,5-dithiolate (isotrithione-dithiolate, dmit) (159), introduced by Steimecke and coworkers681 in 1975. It is formed as the main product by chemical (with sodium or potassium)681,682 or electrochemical reduction683 of CS2 in DMF (reaction 166). 

The most frequently used designation dmit (dimercaptoisotrithione) for the ligand (83) may not be the best choice (the name ethylenetrithiocarbonatedithiolate or trithionedithiolate would seem more appropriate and l,3-dithiol-2-thione-4,5-dithiolate would seem accurate), but it has established itself throughout this corner of the chemical literature. 

The complexes [Ln(dmit)(phen)2Cl3] ", where Ln = Y, La, Nd, Sm, Gd or Er dmit = l,3-dithiole-2-thione-4,5-dithiolate anion, have vLnN in the range... 

The complexes [Ln(dmit)(phen)2Cl3] -, where Ln = La, Nd, Sm, Gd, Er or Y, dmit - = l,3-dithiole-2-thione-4,5-dithiolate anion, have IR bands showing bi-dentate coordination of the dmit (vCS near 1050, 1030 cm-i vCC near 1380 and 1345 cm 1).46 7 Resonance enhancement of Raman bands for Sm(SePh)3 and Yb(SePh)3 (850-950 cm-i) can be ascribed to vibronic coupling between phenyl modes and a CT transition 468... 

Kusamoto T, Yamamoto HM, Tajima N, Oshima Y, Yamashita S, Kato R (2012) Bilayer Mott system based on Ni(dmit)2 (dmit =l,3-dithiole-2-thione-4,5-dithiolate) anion radicals two isostructural salts exhibit contrasting magnetic behavior. Inorg Chem 51 11645-11654... 

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