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Cyanide-bridged [Co(II)2M(II)] and [Co(II)2M(II)2] complexes based on the [Co(II)(triphos)(CN)2] building block: syntheses, structures, magnetic properties, and density functional theoretical studies.

Authors
  • Karadas, Ferdi
  • Shatruk, Michael
  • Perez, Lisa M
  • Dunbar, Kim R
Type
Published Article
Journal
Chemistry - A European Journal
Publisher
Wiley (John Wiley & Sons)
Publication Date
Jun 25, 2010
Volume
16
Issue
24
Pages
7164–7173
Identifiers
DOI: 10.1002/chem.201000128
PMID: 20486105
Source
Medline
License
Unknown

Abstract

Two families of cationic cyanide-bridged complexes, namely, {[Co(triphos)(CN)(2)](2)[M(MeOH)(4)]}(ClO(4))(2) ([Co(2)M] M=Mn, Fe, Co, and Ni; triphos=1,1,1-tris((diphenylphosphino)methyl)ethane) and {[Co(triphos)(CN)(2)](2)[M(MeOH)(4)](2)}(ClO(4))(4) ([Co(2)M(2)] M=Mn and Ni) have been prepared from reactions of [Co(II)(triphos)(CN)(2)] and M(ClO(4))(2).6H(2)O (M=Mn, Fe, Co, Ni) in methanol. The trinuclear complexes [Co(2)Mn], [Co(2)Fe], and [Co(2)Co], as well as both new tetranuclear complexes [Co(2)Mn(2)] and [Co(2)Ni(2)], exhibit antiferromagnetic coupling between metal centers. In contrast, the [Co(2)Ni] is characterized by ferromagnetic interactions between the Co(II) and Ni(II) centers. The magnetic behavior for these complexes was investigated by DFT calculations and was found to derive from overlap patterns of the different magnetic orbitals as influenced by the angles of the cyanide bridges.

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