Complex thiones

The preparation of a series of transition metal complexes (Co. Ni. Pd. Pt, Ir. Au. Cu. Ag) with ambident anion (70) and phosphines as ligands has been reported recently (885). According to the infrared and NMR spectra the thiazoline-2-thione anion is bounded through the exocyclic sulfur atom to the metal. The copper and silver complexes have been found to be dimeric. 

Triazine-3-thione, 5,6-diphenyl-Friedel-Crafts reaction, 3, 409 metal complexes, 3, 456... 

The authors claim that these associations, which are destroyed in fixed compounds, play an important role in the calculation of Ty.The cases of 1,2,4-triazole-5-thiones 74 [97SA(A)699] and of pyridone dimers 15a-15a and 15a-15b were also studied [96MI(13)65]. (3) The recording of IR spectra in solution at different temperatures to determine the effect of the temperature on Kj-, for instance, in pyrazolinones [83JPR(325)238] and in cytosine-guanine base pairs [92MI(9)881]. (4) The determination of the equilibrium 2-aminopyridine/acetic acid 2-aminopyridinium acetate (see Section III.E) in the acid-base complex was carried out by IR (97NKK100). 

Amino-3-methyl-5-thione-l,2,4-triazole with [HgR(MeCOO)] (R = Me, Ph) gives complexes 186, where coordination occurs via the sulfur and amino nitrogen atoms (93JOM(450)41). In the crystalline state, intermolecular interaction of the mercury site with the endocyclic nitrogen atom of the neighboring unit is also observed. 

In the rhodium and iridium complexes, the C-coordination, carbene function, and cyclometallated cases prevail. Benzothiazole-2-thione was studied extensively as a ligand and various situations of the exocyclic S-monodentate coordination as well as N,S-combinations in the di-, tri-, and tetranuclear species were discovered. 

Evans et al. reported that the bis(imine)-copper (II) complex 25, prepared from chiral bis(imine) ligand and Cu(OTf)2, is also an effective chiral Lewis acid catalyst [34] (Scheme 1.44, Table 1.18). By tuning the aryl imine moiety, the bis(2,6-dichlor-ophenylimine) derivative was found to be suitable. Although the endojexo selectivity for 3-alkenoyloxazolidinones is low, significant improvement is achieved with the thiazolidine-2-thione analogs, for which both dienophile reactivity and endojexo selectivity are enhanced. 

Formation constants of Ag(I) complexes with 5,7-dimethyl-4a,7a-diphenyloctahydroimidazo[4,5-e][triazin-6-one-3-thione was determined potentiometrically (79MI2). 

Unlike 2-thiazolidinethione and its simpler derivatives, the 3 - alkyl - 5 - hydroxy - 5 - (1,2,3,4 - tetrahydroxy -n- butyl) - 2 - thiazoli-dine thiones [which are specific, photometric reagents for Cu(ID] undergo rearrangement in the presence of Cu(II) ions, to form complexes of dithiocarbamate. The analytical specificity is explained by the inability of most other metal ions to effect this rearrangement (419). 

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. 

Figure 3.7 Complex obtained by reaction of [Au(C6F5)(tht)] with 4-methyl-3H-thiazole-2-thione.

Neutral Au(I) pentafluorophenyl complexes with heterocyclic thiones can be prepared by displacement of the tht ligand in [Au(QF5)(tht)] with a thione [49] as shown in Equation 3.6. 

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