l-Oxa-4,6-Dithia-5-Arsocane and 1,3,6-Trithia-2-Arsocane Dithiocarbamates Competition Between Transannular and Exocyclic Secondary Bonding to Arsenic

Abstract

1-oxa-4,6-dithia-5-arsocane morpholinyldithiocarbamate (1) and 1,3,6-trithia-2-arsocane 2-diethyldithiocarbamate (2) have been prepared by reacting the corresponding sodium dithiocarbamates with 1-oxa-4,6-dithia-5-arsocane or 1,3,6-trithia-2-arsocane. (1) and (2) were characterized by elemental analyses, IR, MS, ¹H and ¹³C NMR. The X-ray single-crystal molecular structures of (1) [monoclinic, a = 9.931 (5), b = 18.253(5), c = 8.076(3) Å; β = 92.56(2)°; V = 1462.5(7) ų; space group P2₁/c; Z = 4; R = 4.33%] and (2) [monoclinic, a = 7.830(2), b = 10.465(2), c = 19.025(6) Å; β = 95.82(2)°; V = 1550.8(10) ų; space group P2₁ / c; Z = 4; R = 3.41%], show that the compounds are monomeric and contain an asymmetric monometallic biconnective dithiocarbamate ligand with a large distortion in the geometry around the As and a weak heterocyclic arsocane transannular secondary interaction.