Accessibility of manganese oxidation states. Control by pentaaza macrocyclic ligands

James C. Dabrowiak, Laurence A. Nafie, Philip S. Bryan, Andrew T. Torkelson

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The synthesis and characterization of a series of manganese(II) and -(III) and zinc(II) complexes with 15-17-membered pentaaza and 14-membered tetraaza macrocyclic ligands are reported. Except for two of the complexes with the largest ring, [17]pydieneN5, all of the divalent compounds incorporating the pentadentate ligands appear to exhibit pentagonal-type coordination geometry in the solid state. Solution infrared and NMR studies (1H and 13C) on the diamagnetic Zn(II) complexes indicate that in solution all of the pentadentate ligands display a pentagonal coordination geometry. The Mn(II) complexes with the 15-membered pentadentate ligand can be oxidized by NOPF6 to stable Mn(III) products. The pentagonal-bipyramidal coordination geometry displayed by the new complexes is highly unusual and has not been previously observed for Mn(III). These high-spin d4 complexes are deeply colored and exhibit d-d spectra which have been interpreted using a simple one-electron model. The accessibility of the trivalent oxidation state as a function of ligand structure is discussed.

Original languageEnglish (US)
Pages (from-to)540-544
Number of pages5
JournalInorganic Chemistry
Volume16
Issue number3
StatePublished - 1977

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Manganese
manganese
Ligands
Oxidation
ligands
oxidation
Geometry
geometry
Zinc
zinc
Nuclear magnetic resonance
Infrared radiation
solid state
nuclear magnetic resonance
Electrons
rings
synthesis
products
electrons

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Dabrowiak, J. C., Nafie, L. A., Bryan, P. S., & Torkelson, A. T. (1977). Accessibility of manganese oxidation states. Control by pentaaza macrocyclic ligands. Inorganic Chemistry, 16(3), 540-544.

Accessibility of manganese oxidation states. Control by pentaaza macrocyclic ligands. / Dabrowiak, James C.; Nafie, Laurence A.; Bryan, Philip S.; Torkelson, Andrew T.

In: Inorganic Chemistry, Vol. 16, No. 3, 1977, p. 540-544.

Research output: Contribution to journalArticle

Dabrowiak, JC, Nafie, LA, Bryan, PS & Torkelson, AT 1977, 'Accessibility of manganese oxidation states. Control by pentaaza macrocyclic ligands', Inorganic Chemistry, vol. 16, no. 3, pp. 540-544.
Dabrowiak JC, Nafie LA, Bryan PS, Torkelson AT. Accessibility of manganese oxidation states. Control by pentaaza macrocyclic ligands. Inorganic Chemistry. 1977;16(3):540-544.
Dabrowiak, James C. ; Nafie, Laurence A. ; Bryan, Philip S. ; Torkelson, Andrew T. / Accessibility of manganese oxidation states. Control by pentaaza macrocyclic ligands. In: Inorganic Chemistry. 1977 ; Vol. 16, No. 3. pp. 540-544.
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