Palladium xanthates

The alkali metal xanthates react with the lower alkylamines ia the presence of catalytic amounts of nickel or palladium salts to give dialkjdthionocarbamates (62) ... 

Following the successful synthesis of the aryl xanthate complexes, Chen and Fackler reported on the synthesis and structural characterization of the diamagnetic, monomeric bis(0-2,4,6-trimethylphenylxanthato)palladium(II) complex (117). A typical PdS4 unit was found in this complex in which the shorter S2C-0 bond length [1.330(12) A] compared to the Ph-0 bond length [ 1.439(16)] indicates a certain importance of the S2C=6 resonance form in the structure of the xanthate ligand. 

VIII. XANTHATE STRUCTURES OF NICKEL, PALLADIUM, AND PLATINUM 167... 

There has been a review of the use of transition-metal catalysts in the formation of C—S, C—Se, and C—Te bonds." Copper catalysis enables the formation of unsymmetrical diaryl thioethers from two differently substituted aryl iodides using ethylxanthogenate as the source of sulfur. Initial formation of an aryl xanthate, such as (17), is followed by hydrolysis to the arenethiolate, which couples with the second aryl iodide." Copper catalysis has also been used in the methylthiolation of aryl halides by DMSO. The method requires the presence of a source of fluoride ions, such as zinc fluoride." In the presence of a palladium catalyst, the reaction of aryl and heteroaryl bromides with AgSCp3 gives the corresponding trifluoromethylsulfldes." ... 

It was recently reported that a new synthetic route of thiocarbamate was developed. The new synthetic route refers to that thiocarbamate is directly synthesized by the reaction of aliphatic amine and xanthate in the presence of nickel salt or palladium salt. 

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