Oxygenation of zinc dialkyldithiocarbamate complexes: isolation, characterization, and reactivity of the stoichiometric oxygenates

S-oxygenation of dithiocarbamate (DTC) complexes has been implicated in their function as industrial anti-oxidants, as well as in their use as pesticides and most recently in their cumulative toxicity, but little is known of the species generated. Several S-oxygenated derivatives of N,N-disubstituted DTCs have been synthesized, characterized by a variety of methods, and their structure and reactivity examined. Low-temperature reaction of bis(N,N-diethyldithiocarbamato)zinc(II), Zn(deDTC)2 1, with oxygenating reagents (hydrogen peroxide, m-chloroperbenzoic acid, urea hydrogen peroxide) yields mono-oxygenated DTC complexes (N,N-peroxydiethyldithiocarbamato)(N,N-diethyldithiocarbamato)zin(II), Zn(O-deDTC)(deDTC), 2 and bis(N,N-peroxydiethyldithiocarbamato)zinc(II), Zn(O-deDTC)2, 3. The tetraoxygenated derivative bis(N,N-diethylthiocarbamoylsulfinato)zinc(II), Zn(O(2)-deDTC)2, 4, was cleanly obtained by initial reaction of the DTC salts with stoichiometric oxidant prior to complexation with Zn(II). X-ray crystallographic analysis of 2, 3, and 4 show that the peroxydithiocarbamate ligands are S,O-bound. Similar derivatives were obtained from the homoleptic dimethyl and pyrollidine DTC Zn complexes. These oxygenated species display unique 1H and 13C NMR variable-temperature spectra, as the symmetry of DTC ligand is broken upon oxygenation; total line shape analysis (TLSA) was used to compare the energetic parameters for rotation about the C-N bond in several derivatives. Compounds 2, 3, and 4 were deoxygenated by alkyl phosphine, regenerating the parent dithiocarbamate 1. The peroxydithiocarbamate complexes were susceptible to base-catalyzed hydrolytic decomposition, giving ligand-based products indicative of S-oxidation and S-extrusion.     

Nielsen coincidence,fixed point and root theories of n-valued maps

Let ${(\phi, \psi)}$ be an (m, n)-valued pair of maps ${\phi, \psi : X \multimap Y}$ , where ${\phi}$ is an m-valued map and ${\psi}$ is n-valued, on connected finite polyhedra. A point ${x \in X}$ is a coincidence point of ${\phi}$ and ${\psi}$ if ${\phi(x) \cap \psi(x) \neq \emptyset}$ . We define a Nielsen coincidence number ${N(\phi : \psi)}$ which is a lower bound for the number of coincidence points of all (m, n)-valued pairs of maps homotopic to ${(\phi, \psi)}$ . We calculate ${N(\phi : \psi)}$ for all (m, n)-valued pairs of maps of the circle and show that ${N(\phi : \psi)}$ is a sharp lower bound in that setting. Specifically, if ${\phi}$ is of degree a and ${\psi}$ of degree b, then ${N(\phi : \psi) = \frac{|an - bm|}{\langle m, n \rangle}}$ , where ${\langle m, n \rangle}$ is the greatest common divisor of m and n. In order to carry out the calculation, we obtain results, of independent interest, for n-valued maps of compact connected Lie groups that relate the Nielsen fixed point number of Helga Schirmer to the Nielsen root number of Michael Brown.