Dithiolato complexes synthesis

Metal complexes of 1,1-dithiolates have been reviewed by Coucou-vanis (1) Eisenberg (2) presented a systematic, structural review of dithiolato chelates, and Stokolosa ct al. (3) reviewed dithiophosphate complexes in detail. Earlier reviews (4-3) covered less recent work in greater detail. Following initial work by Delepine (9), 1,1-dithiolato complexes were more intensively studied between 1930 and 1941 (10-16). There is, however, continuous interest in the synthesis, characterization, electronic structures, and bonding of these complexes. 

One area of silver chemistry that has received much recent attention is the synthesis of multinuclear aggregates.315 Anionic metal dithiolato complexes such as K M(S2C202)2 were found to form adducts with silver(I) phosphines. In these complexes, the inert cations (K+) that accompanied the metallothio anions could be readily substituted by coordinatively unsaturated silver phosphines Ag(PR3)2. For dithiooxalto complexes this led to the isolation of a remarkable range of linkage isomers (34)-(37) 316,317... 

In the synthesis of the parent dithiolenes, the reaction of the disodium salt of ethylene-cts-dithiolate with metal salts is the only useful method.15 For the preparation of substituted dithiolenes the use of substituted ethylenedithiolates is the most efficient choice. In the synthesis of 1,2-dicyanoethylene-l,2-dithiolato ( mnt ) complexes, it is the only available method.16... 

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