title: Metal-metal bond or isolated metal centers? Interaction of Hg(CN)2 with square planar transition metal cyanides.
abstract: Three adducts have been prepared from Hg(CN)(2) and square planar M(II)(CN)(4)(2)(-) transition metal cyanides (M = Pt, Pd, or Ni, with d(8) electron shell) as solids. The structure of the compounds K(2)PtHg(CN)(6).2H(2)O (1), Na(2)PdHg(CN)(6).2H(2)O (2), and K(2)NiHg(CN)(6).2H(2)O (3) have been studied by single-crystal X-ray diffraction, XPS, Raman spectroscopy, and luminescence spectroscopy in the solid state. The structure of K(2)PtHg(CN)(6).2H(2)O consists of one-dimensional wires. No CN(-) bridges occur between the heterometallic centers. The wires are strictly linear, and the Pt(II) and Hg(II) centers alternate. The distance d(Hg)(-)(Pt) is relatively short, 3.460 A. Time-resolved luminescence spectra indicate that Hg(CN)(2) units incorporated into the structure act as electron traps and shorten the lifetime of both the short-lived and longer-lived exited states in 1 compared to K(2)[Pt(CN)(4)].2H(2)O. The structures of Na(2)PdHg(CN)(6).2H(2)O and K(2)NiHg(CN)(6).2H(2)O can be considered as double salts; the lack of heterometallophilic interaction between the remote Hg(II) and Pd(II) atoms, d(Hg)(-)(Pd) = 4.92 A, and Hg(II) and Ni(II) atoms, d(Hg)(-)(Ni) = 4.61 A, is apparent. Electron binding energy values of the metallic centers measured by XPS show that there is no electron transfer between the metal ions in the three adducts. In solution, experimental findings clearly indicate the lack of metal-metal bond formation in all studied Hg(II)-CN(-)-M(II)(CN)(4)(2)(-) systems (M = Pt, Pd, or Ni).
authors.affiliation: Department of Inorganic and Analytical Chemistry, University of Debrecen, H-4010 Debrecen Pf. 21, Hungary.
authors.forename: Róbert
authors.initials: R
authors.lastname: Jószai
authors.forename: Imre
authors.initials: I
authors.lastname: Beszeda
authors.forename: Attila C
authors.initials: AC
authors.lastname: Bényei
authors.forename: Andreas
authors.initials: A
authors.lastname: Fischer
authors.forename: Margit
authors.initials: M
authors.lastname: Kovács
authors.forename: Mikhail
authors.initials: M
authors.lastname: Maliarik
authors.forename: Péter
authors.initials: P
authors.lastname: Nagy
authors.forename: Andrey
authors.initials: A
authors.lastname: Shchukarev
authors.forename: Imre
authors.initials: I
authors.lastname: Tóth