Transition metal induced derivatisations resulting in novel coordination behaviour of bis(oxamato) ligands

Dalton Trans. 2008 Oct 7:(37):5089-98. doi: 10.1039/b804382e. Epub 2008 Aug 27.

Abstract

Two mononuclear bis(oxamato) complexes with the formula [nBu4N]2[M(2,3-acbo)] (M=Ni (), Cu (), with acbo=anthra-9,10-chinone-2,3-bis(oxamato) have been synthesized starting from symmetric diethyl N,N'-anthra-9,10-chinone-2,3-bis(oxamate) (, 2,3-acboH2Et2). The crystal structures of and have been determined, verifying that the transition metal ions are eta4(kappa2N,kappa2O) coordinated by the [2,3-acbo]4- ligands. Using the asymmetric diethyl N,N'-anthra-9,10-chinone-1,2-bis(oxamate) (, 1,2-acboH2Et2) leads, under otherwise identical reaction conditions, to the novel bis(oxamato) complex [(n)Bu4N]2[Ni(1,2-acbo)] () whereby in the case of Cu(II) the derivate [nBu4N]2[Cu(aibo)2] () (aibo=anthra[1,2-d]-(imidazole-2-carboxylato)-6,11-dione) has been obtained. The crystal structures of and have been determined, displaying that the Ni(II) ion of is eta4(kappa2N,kappa2O) coordinated by the [1,2-acbo]4- ligand. The Cu(II) ion of is coordinated by two [aibo]2- ligands, giving rise to an approximately square-planar trans-bis(aibo-N,O) arrangement. Using the symmetric diethyl N,N'-4,5-dinitro-o-phenylene-bis(oxamate) (, niboH2Et2), possessing strongly electron withdrawing NO2-groups, leads under otherwise identical reaction conditions to the bis(oxamato) complex [nBu4N]2[Ni(nibo)] (), whereby in the case of Cu(II) the derivate [nBu4N]2[Cu(niqo)2] () (niqo=7,8-dinitro-2,3-quinoxalinedionato) has been obtained. The crystal structures of and have been determined, ensuring that the Ni(II) ion of is eta(4)(kappa2N,kappa2O) coordinated by the [nibo]4- ligand. The Cu(II) ion of is coordinated by four oxygen atoms of two [niqo]2- ligands, giving rise to an approximately square-planar coordination geometry.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anthracenes / chemistry*
  • Crystallography, X-Ray
  • Hydrogen Bonding
  • Ligands
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry
  • Oxamic Acid / analogs & derivatives*
  • Oxamic Acid / chemistry*
  • Stereoisomerism
  • Transition Elements / chemistry*

Substances

  • Anthracenes
  • Ligands
  • Organometallic Compounds
  • Transition Elements
  • diethyl N,N'-anthra-9,10-chinone-2,3-bis(oxamate)
  • Oxamic Acid