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Issue 2, 2009
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A MnII4cubane and a novel MnII10MnIII4cluster from the use of di-2-pyridyl ketone in manganese acetate chemistry

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Abstract

The employment of di-2-pyridyl ketone, (py)2CO, in manganese(II) acetate chemistry is reported. The syntheses, crystal structures and magnetochemical characterisation are described for [MnII4(O2CMe)4{(py)2C(OH)O}4] (1) and [MnII10MnIII4O4(O2CMe)20{(py)2C(OH)O}4] (2), where (py)2C(OH)O is the monoanion of the gem-diol form of the ligand. The reaction of Mn(O2CMe)2·4H2O with one equivalent of (py)2CO in Me2CO gives 1. Complex 2 was obtained from the 1 : 1 reaction, in EtOH, between Mn(O2CMe)2·4H2O and (py)2CO in the presence of NEt3. The tetranuclear molecule 1 has a cubane topology with the MnII and the deprotonated oxygen atoms from the η1313 ligands occupying alternate vertices of the cube. The core of 2 consists of two mixed valence cubane {MnII2MnIII23-O)23-OR″)2}4+ subunits that are linked through an unusual {MnII612:μ-O2CMe)6223-O2CMe)2}4+ moiety via twelve η11:μ MeCO2groups. Some suggestions have been made concerning the possible assembly of 2 from 1. The magnetic properties of 1 in the 300–5 K range have been modelled with two J values, which reveal weak antiferromagnetic interactions within the molecule. Complex 2 has a low spin ground state. This work demonstrates the flexibility, versatility and synthetic potential of combining (py)2CO with carboxylate ligands.

Graphical abstract: A MnII4cubane and a novel MnII10MnIII4cluster from the use of di-2-pyridyl ketone in manganese acetate chemistry

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Publication details

The article was received on 26 Jun 2008, accepted on 17 Sep 2008 and first published on 06 Nov 2008


Article type: Paper
DOI: 10.1039/B810835H
Citation: Dalton Trans., 2009, 307-317
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    A MnII4cubane and a novel MnII10MnIII4cluster from the use of di-2-pyridyl ketone in manganese acetate chemistry

    C. C. Stoumpos, I. A. Gass, C. J. Milios, N. Lalioti, A. Terzis, G. Aromí, S. J. Teat, E. K. Brechin and S. P. Perlepes, Dalton Trans., 2009, 307
    DOI: 10.1039/B810835H

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