Heteroleptic platinum(II) complexes with crown thioethers and diimine ligands: The crystal structures of [Pt(9S3)(2,2′-bipy)](PF 6)2 and [Pt(9S3)(4,4-dimethyl-2,2′-bipy)](PF 6)2 · 2.5CH3NO2

Gregory J. Grant, Ketankumar N. Patel, Monte L. Helm, Larry F. Mehne, David W. Klinger, Donald G. Vanderveer

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27 Citations (Scopus)


We wish to report the synthesis, crystal structures, spectroscopic and electrochemical properties of new Pt(II) heteroleptic complexes with two diimines (2,2-bipyridine, 4,4-dimethyl-2, 2-bipyridine), and the crown trithioether 9S3 (1,4,7-trithiacyclononane). In addition, we report the synthesis and spectroscopic properties of three related 9S3/diimine (4,4-di- t-butyl-2,2-bipyridine, 4,4-dinonyl-2,2 -bipyridine, 3,4,7,8-tetramethyl-1,10-phenanthroline) complexes as well as an examination of the spectroscopic and electrochemical properties of the reported [Pt(9S3)(1,10-phenanthroline)](PF6) 2. All complexes have the general formula [Pt(9S3)(N 2)](PF6) (N2 = diimine) and form similar structures in which the Pt(II) center is surrounded by a cis arrangement of the two N donors from the diimine chelate and two sulfur atoms from the 9S3 ligand. The 195Pt NMR chemical shifts for all six complexes show a value near -3290 ppm, consistent with a cis-PtS2N2 coordination sphere. The third sulfur in each structure forms a longer interaction with the platinum resulting in an elongated square pyramidal structure. These distances, however, are approximately 0.2 Å longer than with the analogous diphosphine complexes, demonstrating that better π acids, in fact, do not result in shorter Pt-S axial distances as has previously been proposed.

Original languageEnglish
Pages (from-to)1361-1369
Number of pages9
Issue number8
Publication statusPublished - May 6 2004


  • Crown thioethers
  • Diimine complexes
  • Platinum complexes
  • Platinum nuclear magnetic resonance
  • Thioether complexes
  • Trithiacyclononane

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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