Metal dithiocarbamates, oxidized

Reverse reactions, in which the disulfides are reduced and S—S bond breaking takes place, are also possible. So thiuram disulfide reacts with elemental Cu or Ag yielding the metal dithiocarbamates, and (109) can be oxidized with thiuram disulfide to (110) and (111) to (112). 

The second general method for making polymer materials photo-chemically degradable is to mix a radical initiator into the polymer. Once carbon-based radicals have formed, the chains degrade by the autoxidation cycle (Scheme 2). Numerous radical initiators have been investigated, and a partial list includes metal dithiocarbamates,8 metal oxides (e.g., Ti02, ZnO, CuO), metal chlorides (e.g., LiCl, FeCl3), M(acac) complexes, M (stearate), complexes, benzophenone, quinones, and peroxides.1,2... 

Oxidized Metal Dithiocarbamates. One of the most intriguing developments in recent years in the chemistry of CS2 derivatives is the exceptional ability of the N,N -dialkyldithiocarbamate ligand to stabilize complexes in which the metal is in a high formal oxidation state. The... 

Schoener, D. F. Olsen, M. A. Cummings, P. G. Basic, C. Electrospray ionization of neutral metal dithiocarbamate complexes using in-source oxidation. J. Mass Spectrom. 1999, 34, 1069-1078. 

Transition metal dithiocarbamate complexes were probably first prepared in 1907 by Delepine (2) and over the following century, dithiocarbamate complexes of all the transition elements have been prepared and in a wide range of different oxidation states (Table 1). Perhaps most impressive is their ability to stabilize molybdenum in seven oxidation states ranging from - -6 to 0 (Fig. 24). 

Casey and Vecchio (186,187) developed the oxidative-addition of thiuram disulfides to metals in order to produce a one-step preparation of a wide range of transition metal dithiocarbamate complexes. In this way, [Ni(S2CNMe2)2] and [Zn(S2CNMe2)2] can be prepared in near quantitative yields. With copper, only the copper(II) species are seen, and this is in keeping with Akerstrom s (188) earlier observation that copper(I) species react instantaneously with thiuram disulfides to generate the analogous copper(II) complexes. 

Titanium and zirconium dithiocarbamates are prepared with the metal in the oxidation state + 4, whereas the hafnium dithiocarbamato chemistry is unknown. 

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