Manganese and zinc complexes incorporating an unsaturated cyclic Schiff base ligand

David R. Neves, James C. Dabrowiak

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Abstract

A number of manganese(II) and -(III) as well as two zinc(II) complexes with the conjugated cyclic Schiff base, H2[14] 12eneN4, have been synthesized and fully characterized. The high-spin Mn(III) complexes have the stoichiometry Mn(III)[14] 12eneN4X, where X is Cl-, Br-, SCN-, and N3-. The compounds are intensely colored and exhibit a number of electronic transitions which appear to be associated with the ligand framework. The reduced magnetic moment of the azide derivative suggests that for this complex the Mn(III) ions are linked via an azide bridge in the solid state. Manganese(II) and zinc(II) form five-coordinate complexes with H2[H] 12eneN4 having stoichiometry M(II)[14] 12eneN4(amine), where amine is triethyl-or tri-n-propylamine. NMR studies on the diamagnetic zinc(II) complexes indicate that the sterically hindered tertiary amine is axially coordinated to the metal ion. The distorted five-coordinate geometry is attributed to the mismatch between the relatively large high-spin d5 and d10 metal ions and the hole provided by the macrocyclic ligand. The chemical reactivity of the complexes is also discussed.

Original languageEnglish (US)
Pages (from-to)129-134
Number of pages6
JournalInorganic Chemistry
Volume15
Issue number1
StatePublished - 1976

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Schiff Bases
Manganese
imines
Amines
manganese
Zinc
amines
Azides
zinc
Ligands
Stoichiometry
ligands
Metal ions
stoichiometry
metal ions
Chemical reactivity
Magnetic moments
reactivity
magnetic moments
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Manganese and zinc complexes incorporating an unsaturated cyclic Schiff base ligand. / Neves, David R.; Dabrowiak, James C.

In: Inorganic Chemistry, Vol. 15, No. 1, 1976, p. 129-134.

Research output: Contribution to journalArticle

Neves, David R. ; Dabrowiak, James C. / Manganese and zinc complexes incorporating an unsaturated cyclic Schiff base ligand. In: Inorganic Chemistry. 1976 ; Vol. 15, No. 1. pp. 129-134.
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AB - A number of manganese(II) and -(III) as well as two zinc(II) complexes with the conjugated cyclic Schiff base, H2[14] 12eneN4, have been synthesized and fully characterized. The high-spin Mn(III) complexes have the stoichiometry Mn(III)[14] 12eneN4X, where X is Cl-, Br-, SCN-, and N3-. The compounds are intensely colored and exhibit a number of electronic transitions which appear to be associated with the ligand framework. The reduced magnetic moment of the azide derivative suggests that for this complex the Mn(III) ions are linked via an azide bridge in the solid state. Manganese(II) and zinc(II) form five-coordinate complexes with H2[H] 12eneN4 having stoichiometry M(II)[14] 12eneN4(amine), where amine is triethyl-or tri-n-propylamine. NMR studies on the diamagnetic zinc(II) complexes indicate that the sterically hindered tertiary amine is axially coordinated to the metal ion. The distorted five-coordinate geometry is attributed to the mismatch between the relatively large high-spin d5 and d10 metal ions and the hole provided by the macrocyclic ligand. The chemical reactivity of the complexes is also discussed.

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