AMn II4 cubane and a novel MnII10MnIII4 cluster from the use of di-2-pyridyl ketone in manganese acetate chemistry

Constantinos C. Stoumpos, Ian A. Gass, Constantinos J. Milios, Nikolia Lalioti, Aris Terzis, Guillem Aromi, Simon J. Teat, Euan K. Brechin, Spyros P. Perlepes

Research output: Contribution to journalArticle

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 η1:η3:η1:μ3 ligands occupying alternate vertices of the cube. The core of 2 consists of two mixed valence cubane {MnII2MnIII2(μ3-O)2(μ3-OR'')2}4+ subunits that are linked through an unusual {MnII6(η1:η2:μ-O2CMe)6(η2:η2:μ3-O2CMe)2}4+ moiety via twelve η1:η1:μ MeCO2- groups. 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.
Original languageEnglish
Pages (from-to)307-317
Number of pages11
JournalDalton Transactions
Issue number2
DOIs
Publication statusPublished - 6 Nov 2008

Fingerprint Dive into the research topics of 'AMn II4 cubane and a novel MnII10MnIII4 cluster from the use of di-2-pyridyl ketone in manganese acetate chemistry'. Together they form a unique fingerprint.

  • Cite this

    Stoumpos, C. C., Gass, I. A., Milios, C. J., Lalioti, N., Terzis, A., Aromi, G., Teat, S. J., Brechin, E. K., & Perlepes, S. P. (2008). AMn II4 cubane and a novel MnII10MnIII4 cluster from the use of di-2-pyridyl ketone in manganese acetate chemistry. Dalton Transactions, (2), 307-317. https://doi.org/10.1039/b810835h