Spectroscopic studies, dithiocarbamates complexes

Related to this ketenyl chemistry is the formation of vinylketenes, [W(CO)(S2CNR2)2 rl rl -0=C=C(Ph)CH=CHMe ] (R = Me, Et, Ph) (183), from the aUylidene complex [W(CO)2Br2 q ri - C(Ph)CH=CHMe (4-pico-lene)] (181) and dithiocarbamate salts at 50°C (1096-1098). At lower temperatures four intermediates are observed, spectroscopic studies indicating that each contains an q ri -allyldithiocarbamate ligand generated by dithiocarbamate addition to the mngsten-alkylidene bond. Indeed, in one case such a complex. 

Rice and co-workers (1674) carried out a gas-phase electron diffraction study of [Cu(S2CNMe2)2], for which long-range copper-sulfur interactions are seen in the solid state (1673). They found that it is monomeric in the gas phase, adopting the expected square-planar coordination geometry. Confirmation of the monomeric nature of copper(II) bis(dithiocarbamate) complexes in the gas-phase also comes from mass spectroscopic studies (589). Further, while in the solid state. 

Zinc dithiocarbamates have been used for many years as antioxidants/antiabrasives in motor oils and as vulcanization accelerators in rubber. The crystal structure of bis[A, A-di- -propyldithio-carbamato]zinc shows identical coordination of the two zinc atoms by five sulfur donors in a trigonal-bipyramidal environment with a zinc-zinc distance of 3.786 A.5 5 The electrochemistry of a range of dialkylthiocarbamate zinc complexes was studied at platinum and mercury electrodes. An exchange reaction was observed with mercury of the electrode.556 Different structural types have been identified by variation of the nitrogen donor in the pyridine and N,N,N, N -tetra-methylenediamine adducts of bis[7V,7V-di- .vo-propyldithiocarbamato]zinc. The pyridine shows a 1 1 complex and the TMEDA gives an unusual bridging coordination mode.557 The anionic complexes of zinc tris( V, V-dialkyldithiocarbamates) can be synthesized and have been spectroscopically characterized.558... 

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