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 Helm, Larry F. Mehne, David W. Klinger, Donald G. Vanderveer

Research output: Contribution to journalArticle

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Abstract

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
JournalPolyhedron
Volume23
Issue number8
DOIs
Publication statusPublished - May 6 2004

Fingerprint

Sulfides
Platinum
Crowns
Electrochemical properties
Sulfur
platinum
Crystal structure
Ligands
ligands
crystal structure
Chemical shift
sulfur
Nuclear magnetic resonance
synthesis
chelates
Atoms
Acids
chemical equilibrium
examination
nuclear magnetic resonance

Keywords

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

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

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

In: Polyhedron, Vol. 23, No. 8, 06.05.2004, p. 1361-1369.

Research output: Contribution to journalArticle

Grant, Gregory J. ; Patel, Ketankumar N. ; Helm, Monte ; Mehne, Larry F. ; Klinger, David W. ; Vanderveer, Donald G. / 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. In: Polyhedron. 2004 ; Vol. 23, No. 8. pp. 1361-1369.
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abstract = "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 {\AA} 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.",
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T1 - Heteroleptic platinum(II) complexes with crown thioethers and diimine ligands

T2 - 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

AU - Grant, Gregory J.

AU - Patel, Ketankumar N.

AU - Helm, Monte

AU - Mehne, Larry F.

AU - Klinger, David W.

AU - Vanderveer, Donald G.

PY - 2004/5/6

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N2 - 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.

AB - 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.

KW - Crown thioethers

KW - Diimine complexes

KW - Platinum complexes

KW - Platinum nuclear magnetic resonance

KW - Thioether complexes

KW - Trithiacyclononane

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