A multifrequency high-field EPR (9-285 GHz) investigation of a series of dichloride mononuclear penta-coordinated Mn(II) complexes

Carole Duboc, Vincent Astier-Perret, Hongyu Chen, Jacques Pécaut, Robert H. Crabtree, Gary W. Brudvig, Marie Noëlle Collomb

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Abstract

The electronic structure of a series of 11 penta-coordinated dichloride mononuclear Mn(II) complexes [Mn(L)Cl2] (L = Cl-terpy, Br-terpy, OH-terpy, phenyl-terpy, tolyl-terpy, mesityl-terpy, EtO-terpy, Me 2N-terpy, tBu3-terpy, py-phen, and dpya) has been investigated by a multifrequency EPR study (9-285 GHz). The X-ray structures of [Mn(Br-terpy)Cl2], [Mn(EtO-terpy)Cl2], [Mn(Me 2N-terpy)Cl2] and [Mn(tolyl-terpy)Cl2] are described. The spin Hamiltonian parameters have been determined for all complexes and show that the steric and electronic effects of the N-tridentate ligand L do not induce appreciable variations on the zero field splitting parameters. The magnitude of D, close to 0.3 cm-1, is governed by the chloride anion. High-field EPR spectroscopy allows the determination of electronic parameters of mononuclear Mn(II) complexes characterized by relatively large magnitudes of D and the unambiguous interpretation of the X-band spectra of these kinds of complexes.

Original languageEnglish
Pages (from-to)1541-1548
Number of pages8
JournalInorganica Chimica Acta
Volume359
Issue number5
DOIs
Publication statusPublished - Mar 20 2006

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Keywords

  • Electronic properties
  • High field EPR
  • Mononuclear dichloro-manganese(II) complex
  • Multifrequency EPR spectroscopy
  • N-Tridentate ligand

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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