Metal-metal interactions in platinum(II)/gold(I) or platinum(II)/silver(I) salts containing planar cations and linear anions

Inorg Chem. 2005 May 16;44(10):3466-72. doi: 10.1021/ic048333a.

Abstract

The salts [Pt{C(NHMe)(2)}(4)][Au(CN)(2)](2), [Pt{C(NHMe)(2)}(4)][Ag(2)(CN)(3)][Ag(CN)(2)], [Pt(en)(2)][Au(CN)(2)](2), [Pt(en)(2)][Ag(CN)(2)](2), and [Pt(bipy)(2)][Au(CN)(2)](2) have been prepared by mixing solutions of salts containing the appropriate cation with solutions of K[Au(CN)(2)] or K[Ag(CN)(2)]. Because the platinum atom in the cation is sterically protected, the structures of [Pt{C(NHMe)(2)}(4)][Au(CN)(2)](2) and [Pt{C(NHMe)(2)}(4)][Ag(2)(CN)(3)][Ag(CN)(2)] reveal no close metal-metal interactions. Colorless crystals of [Pt(en)(2)][Au(CN)(2)](2) and [Pt(en)(2)][Ag(CN)(2)](2) are isostructural and involve extended chains of alternating cations and anions that run parallel to the crystallographic a axis, along with isolated anions. In the chains, the metal-metal separations are relatively short: Pt...Au, 3.1799(3) Angstroms; Pt...Ag, 3.1949(2) Angstroms. In [Pt(bipy)(2)][Au(CN)(2)](2), each cation has axial interactions with the anions through close Pt...Au contacts [3.1735(6) Angstroms]. In addition, the anions are weakly linked through Au...Au contacts of 3.5978(9) Angstroms. Unlike the previously reported Pt/Au complex [Pt(NH(3))(4)][Au(CN)(2)](2).1.5H(2)O, which is luminescent, none of the salts reported here luminesce.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Anions / chemistry
  • Cations / chemistry
  • Crystallography, X-Ray
  • Gold / chemistry*
  • Molecular Conformation
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry
  • Platinum / chemistry*
  • Salts / chemical synthesis
  • Silver / chemistry*

Substances

  • Anions
  • Cations
  • Organometallic Compounds
  • Salts
  • Silver
  • Platinum
  • Gold