Trithiocarbonate complexes

The preparation and chemistry of nickel trithiocarbonate complexes have been studied in detail, and both [NKCSs) ] and [Ni(CS4)2 have been isolated (379). Shul man and co-workers (379) reprepared the known [Ni(NH3)3(CS3)]and [Ni(en)3]CS3, and the kinetics of the reaction of Ni(II) with the trithiocarbonate ion in methanol was studied the results confirmed the previously proposed ion-pair mechanism (380). 

Cyclic trithiocarbonate complexes of type le [L = CO, P(OMe)j] (Table I) undergo ring opening on deprotonation (100). Alkylation of the formed anion affords a new type ofcarbene complex, 106, as well as complex 107,... 

The reaction of dithiocarbonate complexes of ruthenium 52 with carbon disulfide affords trithiocarbonate complexes 53. The reaction proceeds via addition across the ruthenium-sulfur bond with generation of 54 and carbonyl sulfide4. ... 

In a similar fashion, alkyl trithiocarbonate complexes react with secondary amines to yield dithiocarbamates with concomitant elimination of the thiol (Eq. 41) (224, 226-228). 

The trithiocarbonato complex anions [M(CS3)212 (M = Zn or Cd) have been isolated as their tetraphenyl-phosphonium and -arsonium salts.881 The trithiocarbonate is bidentate and forms four-membered chelate rings. 

In order to clarify the mechanism, the reaction of carbon disulphide with mercury bis(n-butanethiolate) was studied. On the basis of results obtained, it was suggested that this reaction involved the formation of a coordination complex, followed by the formation of active species containing the Hg-SC(S) bond. Moreover, the cyclic trithiocarbonate, ethylene trithiocarbonate, found to be present in trace amounts in copolymerisation products, was excluded as a possible intermediate for the copolymer formation, since it did not undergo any polymerisation under the given conditions [249],... 

A versatile route to RS-substituted dithiolenes entails S-alkylation of the trithiocarbonate dmit2 (see Section II.C.l), which provides an efficient means to introduction of diverse functionality to the dithiolene backbone. Subsequent to S-alkylation, the resulting S=CS2C2(SR)2 is converted to the dithiocarbonate 0=CS2C2(SR)2 with Hg(OAc)2 in acetic acid (63, 83, 84). Such dithiocarbo-nates are more easily hydrolyzed than the trithiocarbonates (72, 85). This approach has been used for the synthesis of Ni[S2C2(S(CH2) Me)2]2 (n = 2-11) (86) and related complexes with pendant alkene substituents (Eq. 8) (87). 

In a similar reaction, [MoS 412 reacts with C4S5O, the monothiocarbonyl derivative of TPD, to give the same products as above, showing the preferential reactivity of the thiometalate for the dithio- versus the trithiocarbonate. It was also found that the tetrasulfido complex ZnS4(pmdta) (Section III. A) reacts with TPD to give Zn(S2C2S2CO)(pmdta) (189). 

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