Affiliations: Chemistry Division (Code 6120) and Laboratory for the Structure of Matter (Code 6030), Naval Research Laboratory, Washington, DC 20375-5342
Note: [] Corresponding author.
Abstract: A series of anhydrous calcium dithiocarbamates, Ca(S2CNR2)2 (NR2 = NEt2, N(CHMe2)2, NBu2, N(CH2)4, N(H)CMe3, N(H)(CH2)3NMe2), and one strontium dithiocarbamate (Sr(S2CNBu2)2) were synthesized. All compounds were characterized by NMR, IR, and elemental analysis. Thermogravimetric analysis shows the dialkyldithiocarbamates to decompose around 350–400°C and the monoalkyl derivatives to decompose at a lower temperature, 100–150 °C. Only the diisopropyl and the two monoalkyl derivatives decompose cleanly to CaS; all the other dialkyldithiocarbamates decompose to a highly carbonized product. The crystal structures of two dithiocarbamates, Ca(S2CN(CH2)4)2 ((CH2)4NH)2 (3a) and Ca(S2CN(H)(CH2)3NMe2)2 (THF)2·H2O (7a), and a calcium thiocyanate byproduct Ca(NCS)2 (THF)2 (8a) were determined. Crystal data: 3a; Pccn, a = 15.074(5), b = 11.924(4), c = 13.662(5), d(ca1c) = 1.284, Z = 4, 2845 unique data, R = 0.107; 7a, P212121, a = 10.471(4), b = 15.065(6), c = 18.736(11), d(ca1c) = 1.252, Z = 4, 2291 unique data, R = 0.062; 8a, P21/n, a = 7.675(3), b = 10.274(3), c = 15.658(6), β = 96.42(3), d(calc) = 1.204, Z = 2, 2169 unique data, R = 0.126.
