Aspects of the inorganic chemistry of rubber vulcanisation. Part 3. Anionic cadmium complexes derived from dialkyldithiocarbamates, 2-mercaptobenzothiazole and its derivatives, and dialkyl dithiophosphates, and the crystal and molecular structures of [NBun4][Cd(S2CNEt2)3], [NEt4][Cd(C7H4NS2)3], and [NMe4][Cd{S2P(OPri)2}3]

Abstract

The reactions of [Cdl₂{(S₂CNEt₂)₂}] with certain Lewis bases are described, and the complexes [NBuⁿ₄][Cdl₂(S₂CNEt₂)], [NR₄][Cd(S₂CNR′₂)₃](R = Me or Buⁿ; R′= Me, Et, Buⁿ, or NHNMe₂), [NR₄][Cd(OCOMe)(S₂CNEt₂)₂], (R = Me or Buⁿ), [{Cd(S₂CNHNMe₂)₂}_n], [Cd(py)₂(6-RC₇H₃NS₂)₂](R = H or EtO, py = pyridine), [Cd(6-EtOC₇H₃NS₂)₂], [NBuⁿ₄][Cd(C₇H₄NS₂)_n(6-EtOC₇H₃NS₂)_3–n](n= O–3), [NBuⁿ₄][Cd(C₇H₄NS₂)₂(S₂CNEt₂)], and [NMe₄][Cd{S₂P(OPrⁱ)₂}₃] have been prepared. The structures of the title compounds have been determined crystallographically. All three anions have geometries intermediate between trigonalprismatic and octahedral; in the second, the C₇H₄NS₂^– ligand is bound to the metal via the N and the exocyclic S (thiolate) atoms. These structures are compared with those of the corresponding zinc complexes and [Cd(S₂COEt)₃]^–.