Dithiolate complexes sulfur-addition reaction

The significant changes imposed on the dithioaromatic ligands and complexes upon sulfur addition are illustrated in the structure of the Ni(p-/-PrPhDtaXp-(-PrPhDtaS) complex (Fig. 48) (Table XXII), determined by Fackler et al. (233, 257). The same workers explored the sulfur addition and abstraction reaction in depth (232) (see also Section IV). The rates and mechanisms of substitution reactions of square planar nickel(II) 1,1 -dithiolate complexes (502) is discussed in Section IV. 

The question of whether sulfur insertion occurs at the C-S or the M- S bond was raised following the first isolation of the perthio-l,l-dithiolate complexes (156). Early studies of the sulfur-addition and sulfur-abstraction reactions using 33S were reported for Ni(CS3)2" (Eq. 54). It was concluded that the added sulfur was inserted into the C -S bond (156). 

Carbon disulfide reacts with a wide range of bases to produce ligands which readily coordinate to metals. New synthetic work including the formation of aryl xanthates, disulfide products, and oxidized metal dithiolates is reviewed. The sulfur addition and abstraction reactions are discussed, along with the photobleaching reaction of [Ni(n-butyldtc)a] Bridged mercaptide complexes of nickel triad elements are also described. 

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