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Journal of Structural Chemistry

, Volume 48, Issue 2, pp 289–299 | Cite as

Introduction of halogen atoms into gold(III) tetraaza metallocomplexes. Crystal and molecular structure of [Au(C9H18N4Br)](ClO4)2 and [Au(C14H20N4Br2)]ClO4

  • V. A. Afanasieva
  • L. A. Glinskaya
  • R. F. Klevtsova
  • I. V. Mironov
  • L. A. Sheludyakova
Article

Abstract

The utility of the AuX 4 ion (X = Cl, Br) as a mild selective halogenating agent for introducing halogen atoms into the β-position of the six-membered rings of gold(III) tetraaza metallocomplexes is shown. β-Brominated acyclic and macrocyclic compexes of gold(III) have been synthesized: N,N′-bis(2-aminoethyl)-3-bromo-2,4-pentanediiminatogold(III) bisperchlorate (III) and 6,13-dibromo-5,7,12,14-tetramethyl-1,4,8,11-tetraaza-4,6,11,13-tetraenatogold(III) perchlorate (VI). The compounds were defined by element and X-ray phase analyses and by IR and photoelectron spectroscopy; the crystal structures of the compounds have been determined. Monoclinic crystals, III: a = 20.1643(7) Å, b = 7.2932(2) Å, c = 25.5391(9) Å; β = 109.545(1)°, V = 3539.4(2) Å3, Z = 4, space group P21/c; VI: a = 9.9991(3) Å, b = 7.3639(2) Å, c = 12.9242(4) Å; β = 96.922(1)°, V = 944.70(5) Å3, Z = 2, space group P2/c. The structures involve almost planar [Au(C9H18N4Br)]+ cations (III) and [Au(C14H20N4Br2)]+ (VI) and ClO 4 perchlorate anions. In both compounds, the gold atom is surrounded by a plane square of four nitrogen atoms. Introduction of halogen atoms (Cl, Br) into the β-position of the six-membered rings of tetraazametallocycles does not appreciably change the lengths of the delocalized \(C\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdots}$}}{ - } N\) and \(C\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle\cdots}$}}{ - } C\) bonds.

Keywords

gold tetraaza metallocycles β-brominated synthesis crystal and molecular structure electronic spectra IR spectra 

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Copyright information

© Springer Science+Business Media, Inc. 2007

Authors and Affiliations

  • V. A. Afanasieva
    • 1
  • L. A. Glinskaya
    • 1
  • R. F. Klevtsova
    • 1
  • I. V. Mironov
    • 1
  • L. A. Sheludyakova
    • 1
  1. 1.A. V. Nikolaev Institute of Inorganic Chemistry Siberian DivisionRussian Academy of SciencesNovosibirsk

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