Reactivity of zinc dialkyldithiocarbamates towards halogen‐substituted olefins

The reaction of bis(dimethyldithiocarbamato)zinc(II) [Zn(dmtc)2] with halogen-substituted 2,3-dimethyl-2-butene (e.g., 1-bromo-2,3-dimethyl-2-butene; tme-Br) causes substitution of bromide by the dmtc ligands. Depending on the polarity of the solvent, this results either in a complex ZnBr2 (tme-dmtc)2, in which the coupling product remains coordinated to the metal, or in the liberation of the ligand, producing ZnBr2 and tme-dmtc. Crystals of tme-dmtc have been obtained from methanol solution. An X-ray structure of this solid has been determined; relevant data: C9H17NS2, Mr = 204.4, monoclinic, P21, a = 8.2087(5), b = 7.3551(5), c = 10.2791(8) A, β = 106.437(6)°, V = 595.25(8) A3, Z = 2, Dx = 1.14 g·cm−3, λ(CuKα) = 1.5418 A, μ(CuKα) = 36.25 cm−1, F(000) = 222, room temperature. Final R = 0.069 for 853 observed reflections.