Aspects of the inorganic chemistry of rubber vulcanisation. Part 2. Anionic mixed-ligand zinc complexes derived from dialkyldithiocarbamates, 2-mercapto-benzothiazole, -benzoxazole, and -benzimidazole, and the crystal and molecular structures of [NEt4][Zn(S2CNMe2)3], [NBun4][Zn(C7H4NS2)3(OH2)], [NBun4][Zn(S2CNMe2)2(C7H4NS2)]˙C2H5OH, and [NBun4][Zn(S2CNMe2)(C7H4NS2)2]

Abstract

The complexes [Zn(S₂CNR₂)₃]^–(R = Me or Et), [Zn(S₂CNR₂)(S₂CNR′₂)₂]^–[R = Me, Et, or Buⁿ; R′= Me or Et; R₂=(CH₂)₅, R′= Me or Et], [Zn(C₇H₄NS₂)₃(OH₂)]^–(C₇H₄NS₂= benzothiazole-2-thiolate), [Zn(S₂CNR₂)₂(C₇H₄NS₂)]^–[R = Me, Et, or Buⁿ; R₂=(CH₂)₅], [Zn(S₂CNR₂)₂(C₇H₄NOS)]^–[R = Me, Et, or Buⁿ; R₂=(CH₂)₅; C₇H₄NOS = benzoxazole-2-thiolate], [Zn(S₂CNR₂)(C₇H₄NS₂)₂]^–[R = Me, Et, Buⁿ, or C₆H₁₁; R₂=(CH₂)₅], [Zn(S₂CNR₂)(C₇H₄NOS)₂]^–[R = Me or Et; R₂=(CH₂)₅], and [Zn{S₂[graphic omitted]H₂}(C₇H₅N₂S)₂]^–(C₇H₅N₂S = benzimidazole-2-thiolate) have been isolated as their [NMe₄]⁺ and [NBuⁿ₄]⁺salts. The compounds [NR″₄][S₂CNR₂][R″= Me or Buⁿ; R = Et or C₆H₁₁; R₂=(CH₂)₅], [NR″₄][C₇H₄NS₂], [NR″₄][C₇H₄NOS](R″= Me or Buⁿ), [NBuⁿ₄][C₇H₅N₂S], and [NBuⁿ₄][C₃H₄NS₂](C₃H₄NS₂= thiazoline-2-thiolate) have also been prepared. The structures of the four title complexes have been determined crystallographically. The nature of the distortions from regular co-ordination geometries is some of these species are discussed and related to the molecular structures of [{Zn(S₂CNR₂)₂}₂](R = Me or Et).