Synthesis and Characterization of the Bis(diselenolene) Complexes [M(Se2C2(CF3)2)2]z (M = Pt, z = 0, -1, -2; M = Au, z = -1) and Crystal Structure of [(C6H5)4P][Pt(Se2C2(CF3)2)2]

William B. Heuer, Anne E. True, Paul N. Swepston, Brian M. Hoffman*

*Corresponding author for this work

Research output: Contribution to journalArticle

36 Scopus citations

Abstract

New metal diselenolene complexes with the formula [M(Se2C2(CF3)2)2]z (M = Pt, z = 0, -1, -2; M = Au, z = -1) have been prepared by the reaction of bis(trifluoromethyl)diselenete, (CF3)2C2Se2, with (Ph3P)2PtCl2 and (Ph3P)AuCl, respectively; the previously known Ni and Cu analogues have been similarly obtained. Comparison of electrochemical data for these complexes with those of the corresponding metal bis(dithiolene) complexes indicates that substitution of selenium for sulfur does not dramatically alter the electronic structure. Analysis of ESR spectra of the paramagnetic [M(Se2C2(CF3)2)2]- (M = Ni, Pt) anions indicates that the majority (ca. 70%) of the unpaired spin is located on the four selenium atoms. The neutral complex [Pt-(Se2C2(CF3)2)2] exhibits an unusual associational equilibrium in solution that has been studied by UV-vis and 19F NMR spectroscopy. The X-ray crystal structure of [(C6H5)4P] [Pt(Se2C2(CF3)2)2] also is reported; the coordination geometry of Pt is nominally square planar, with interatomic distances reflecting substantial multiple-bond character in the Pt-Se bonds. Crystal data: monoclinic, space group P21/c, with a = 18.015 (3) Å, b = 14.280 (4) Å, c = 14.627 (4) Å, β = 112.30 (2)°, V = 3481.4 (9) Å 3, and Z = 4.

Original languageEnglish (US)
Pages (from-to)1474-1482
Number of pages9
JournalInorganic chemistry
Volume27
Issue number8
DOIs
StatePublished - Apr 1 1988

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Synthesis and Characterization of the Bis(diselenolene) Complexes [M(Se<sub>2</sub>C<sub>2</sub>(CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub>]<sup>z</sup> (M = Pt, z = 0, -1, -2; M = Au, z = -1) and Crystal Structure of [(C<sub>6</sub>H<sub>5</sub>)<sub>4</sub>P][Pt(Se<sub>2</sub>C<sub>2</sub>(CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub>]'. Together they form a unique fingerprint.

  • Cite this