A discrete neutral transition-metal citrate cubane with an M4O4 core; coordinative versatility of the [MII4(citrate)4]8− fragment

Larry R. Falvello; Elena Forcén-Vázquez; Fernando Palacio; Sergio Sanz; Milagros Tomás

doi:10.1039/C4DT01085J

A discrete neutral transition-metal citrate cubane with an M₄O₄ core; coordinative versatility of the [M^II₄(citrate)₄]⁸⁻ fragment†

Larry R. Falvello,*^a Elena Forcén-Vázquez,^a Fernando Palacio,^b Sergio Sanz ‡^a and Milagros Tomás^c

* Corresponding authors

^a Dpto. de Química Inorgánica and I.C.M.A., Universidad de Zaragoza – C.S.I.C., Pedro Cerbuna 12, E-50009 Zaragoza, Spain
E-mail: falvello@unizar.es
Fax: +34 976 761187
Tel: +34 976 761179

^b Dpto. de Física de la Materia Condensada and I.C.M.A., Universidad de Zaragoza – C.S.I.C., Pedro Cerbuna 12, E-50009 Zaragoza, Spain
E-mail: palacio@unizar.es
Fax: +34 976 761229
Tel: +34 976 761227

^c Dpto. de Química Inorgánica and I.S.Q.C.H., Universidad de Zaragoza – C.S.I.C., Pedro Cerbuna 12, E-50009 Zaragoza, Spain
E-mail: milagros@unizar.es

Abstract

The neutral cluster [Mn^II₈(citrate)₄(H₂O)₁₈] is formed by the [M₄(citrate)₄]⁸⁻ fragment, with an Mn₄O₄ cubane core, which bonds four peripheral aquomanganese units – two [Mn(H₂O)₄]²⁺ and two [Mn(H₂O)₅]²⁺ – through a total of six metal–ligand bonds, giving a discrete neutral compound. The compound presents a unique coordination mode in which the citrate cubane acts as a chelate to each of the two peripheral [Mn(H₂O)₄]²⁺ (tetra-aquo) units. A detailed analysis of the central and peripheral geometries is given in terms of the tetrahedral distortions of key structural features. A reversible dehydration–rehydration process has been observed in a polycrystalline sample of the complex, whose structure lacks pores or channels.

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DOI: https://doi.org/10.1039/C4DT01085J
Article type: Communication
Submitted: 11 Apr 2014
Accepted: 15 May 2014
First published: 05 Jun 2014

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Dalton Trans., 2014,43, 10700-10704

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A discrete neutral transition-metal citrate cubane with an M₄O₄ core; coordinative versatility of the [M^II₄(citrate)₄]⁸⁻ fragment

L. R. Falvello, E. Forcén-Vázquez, F. Palacio, S. Sanz and M. Tomás, Dalton Trans., 2014, 43, 10700 DOI: 10.1039/C4DT01085J

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Dalton Transactions

A discrete neutral transition-metal citrate cubane with an M₄O₄ core; coordinative versatility of the [M^II₄(citrate)₄]⁸⁻ fragment†

Abstract

Supplementary files

Article information

Download Citation

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A discrete neutral transition-metal citrate cubane with an M₄O₄ core; coordinative versatility of the [M^II₄(citrate)₄]⁸⁻ fragment

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