Homoleptic Group 12 metal complexes of macrocyclic thioethers: The crystal structures of bis(1,4,7-trithiacyclodecane)M(II) perchlorate: M(II)=zinc(II), cadmium(II), mercury(II)

Monte L. Helm, Charles M. Combs, Donald G. VanDerveer, Gregory J. Grant

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

We wish to report the crystal structures for a series of homoleptic complexes involving the three Group 12 family members with the crown thioether 1,4,7-trithiacyclodecane (10S3). The ligand coordinates in tridentate fashion and readily forms bis complexes with the d10 metal ions, Zn(II), Cd(II), and Hg(II). The three compounds have the general formula [M(10S3)2](ClO4)2 and are isostructural. The three crystal structures show the two 10S3 ligands arranged in a trans or anti fashion around the metal center in a distorted octahedral fashion to yield the meso stereoisomer. All three complexes show hexakis(thioether) octahedral coordination which is unusual for these Group 12 metal ions. The mean M-S bond distances increase as one moves down the family although there is only a modest increase between the Cd and Hg complexes (Zn: 2.4965(10) Å, Cd: 2.6523(6) Å, Hg: 2.6870(16) Å). In sharp contrast to crown thioether complexes of other metal ions, the majority of the M-S bond lengths in these 10S3 complexes are shorter than those found in their 9S3 analogs. A simple four line 13C{1H} NMR spectrum is obtained for the three complexes. Variable temperature 13C{1H} NMR experiments performed on the Hg(II) complex suggest a rapid intermolecular exchange of the 10S3 ligands is occurring. The Cd complex shows a singlet in its 113Cd{1H} NMR spectrum with a chemical shift at 612 ppm, in agreement with a hexakis(thioether) coordination environment.

Original languageEnglish
Pages (from-to)182-188
Number of pages7
JournalInorganica Chimica Acta
Volume338
DOIs
Publication statusPublished - Oct 14 2002

Keywords

  • Cadmium complexes
  • Crystal structure
  • Macrocyclic thioether complexes
  • Mercury complexes
  • Zinc complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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