Journal article
The role of the bridging group in exchange coupling in dinuclear homo- and heterometallic Ni(II) and Co(II) complexes with oxalate, oxamidate and dithiooxamidate bridges
Dalton transactions : an international journal of inorganic chemistry, v 41(37), pp 11319-11329
01 Jan 2012
PMID: 22885878
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Abstract
Six homodinuclear and two heteronuclear complexes Tp(Np)Co-C2O4-CoTp(Np) (1), Tp(Np)Co-C2O4-NiTp(Cy) (2), Tp(Cy)Ni-C2O4-NiTp(Cy) (3), Tp(Np)Co-C2O2(NH)(2)-CoTp(Np) (4), Tp(Cy)Ni-C2O2(NH)(2)-NiTp(Cy) (5), Tp(Np)Co-C2S2(NH)(2)-CoTp(Np) (6), Tp(Np)Co-C2S2(NH)(2)-NiTp(Cy) (7), Tp(Cy)Ni-C2S2(NH)(2)-NiTp(Cy) (8) (Tp(Np) = tris(3-neopentylpyrazolyl)borate, Tp(Cy) = tris(3-cyclohexylpyrazolyl)borate), were synthesized and characterized by mass spectrometry, electronic spectroscopy and X-ray crystallography. These compounds possess similar molecular structures, with the metal ions linked by bridging oxalate (1-3), oxamidate (4 and 5) or dithiooxamidate (6-8) ions. The heteronuclear nature of compounds 2 and 7 was additionally confirmed by high-resolution mass spectrometry. The magnetic properties of the Co2+ complexes were modelled taking into account zero-field splitting of this ion, yielding D-values for Co2+ in the range -17(1) to -50(1) cm(-1). All the metal ion pairs in compounds 1-8 are antiferromagnetically-coupled, with J values between -10.0(1) and -45.0(2) cm(-1) (via the exchange Hamiltonian (H) over cap (ex) = -2J (S) over cap (1)(S) over cap (2)) and vertical bar J vertical bar increasing in the order oxalate < oxamidate < dithiooxamidate. This tendency can be attributed to greater M-S bond covalency compared to M-N or M-O bonds (M = Co2+ and Ni2+). It was found that this antiferromagnetic coupling of Co2+ and Ni2+ ions through oxalate is more efficient for these tris(pyrazolyl) borate complexes than for similar oxalate-bridged systems with neutral aliphatic amine ligands.
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Details
- Title
- The role of the bridging group in exchange coupling in dinuclear homo- and heterometallic Ni(II) and Co(II) complexes with oxalate, oxamidate and dithiooxamidate bridges
- Creators
- Elena A. Mikhalyova - L.V. Pisarzhevskii Institute of Physical ChemistrySergey V. Kolotilov - L.V. Pisarzhevskii Institute of Physical ChemistryOlivier Cador - University of Rennes 1Matthias Zeller - Youngstown State UniversitySwiatoslaw Trofimenko - University of DelawareLahcene Ouahab - University of Rennes 1Anthony W. Addison - Drexel UniversityVitaly V. Pavlishchuk - L.V. Pisarzhevskii Institute of Physical ChemistryAllen D. Hunter - Youngstown State University
- Publication Details
- Dalton transactions : an international journal of inorganic chemistry, v 41(37), pp 11319-11329
- Publisher
- Royal Soc Chemistry
- Number of pages
- 11
- Grant note
- Youngstown State University 0087210 / NSF; National Science Foundation (NSF) Drexel University PAI NASU-CNRS exchange program CAP-491 / Ohio Board of Regents
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000308361400012
- Scopus ID
- 2-s2.0-84872039732
- Other Identifier
- 991019168057804721
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear