Influence of the Counteranion on the Formation of Polymeric Networks by Metal Complexes of Hexamethylenebis(acetamide)

Chatterton, Nicholas P.; Goodgame, David M. L.; Grachvogel, David A.; Hussain, Izhar; White, Andrew J. P. and Williams, David J. (2001). Influence of the Counteranion on the Formation of Polymeric Networks by Metal Complexes of Hexamethylenebis(acetamide). Inorganic Chemistry, 40(2) pp. 312–317.

DOI: https://doi.org/10.1021/ic000673i

Abstract

An investigation into the anion dependence of the network-forming ability of metal complexes of hexamethylenebis(acetamide), CH3 CONH(CH2)6NHCOCH3 (HMBA), has resulted in the X-ray characterization of the compounds [Co(HMBA)3][Co(NCS)4], 1, [Nd(HMBA)3][Nd(NO3)6]·2CHCl3, 2, [Co(HMBA)3][HgCl4], 3, and [Mn(HMBA)3][HgBr4]·3CHCl3, 4. The structures of compounds 1, 3, and 4 each comprise cationic frameworks formed by the bridging action of HMBA ligands binding octahedrally to the cobalt or manganese centers and, in the cases of 3 and 4, the formation of tetrahedral HgX42- anions by transfer of the respective halide ions from Co or Mn to Hg. Complete anion (NO3-) transfer between Nd centers is also a key factor in the structure of 2, which forms a cationic 3-D network of HMBA-bridged octahedrally coordinated Nd centers with occluded [Nd(NO 3)66]3- anions. These types of inter-metal-anion transfer, with consequent complex counteranion formation, appear to facilitate the network-forming ability of the metal−HMBA cationic arrays.

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