Zirconium, dithiocarbamate complexes

Two recent papers on [(jj-C5H5)M(S2CNMe2)3] (M = Zr or Hf) and [(rj-C5H5)2ZrCl(S2CNR2)] (R = Me or Et) are mentioned in passing to provide an entry into the current literature on organo-zirconium and -hafnium dithiocarbamate complexes. 

Group 4 (IV B) dithiocarbamate chemistry is constrained to the 4-4 oxidation state. The first reported example was the eight-coordinate tetrakis(dithiocarba-mate) titanium complex, [Ti(S2CNBz2)4], prepared by Dermer and Femelius in 1934 (608), while the heavier zirconium and hafnium analogues were first prepared by Bradley and Gitlitz (193) from the reaction of metal amides, [M(NR2)4] (M = Ti, Zr, Hf), with carbon disulfide. 

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