Inorganic Ozonides

Inorganic ozonides are compounds containing the radical anion O₃^–, a 19-valence- electron anion, showing a conspicuous red color. Due to extreme air-, moisture- and temperature sensitivity, gram amounts of pure alkali ozonides have been synthesized not until 1985, starting from alkali hyperoxides and ozone.^[1] This procedure permits the synthesis of the higher alkali ozonides (K – Cs), the starting materials of any further ozonide chemistry.^[2]
All other ozonide compounds require other/new synthesis routes e.g. metathesis reactions^[3] or ion exchange.^[4]

An ozonide crystal sealed in a capillary.[3]

Meanwhile, the field of ozonides has been expanded to: alkaline-earth metals Cs2Ba(O3)4•2NH3[5] and Sr(O3)2•9NH3[6] several organic cations and bications e.g. (NMe4)O3 (see figure right),[3], (PMe4)O3[7], (Me3N(CH2)3NMe3)(O3)2[8] ozonides, soluble in organic solvents e.g. (Bu4N)O3[9], Rb([18]crown-6)O3•NH3[10]

Recent results:

• Cs₅([12]crown-4)₂(O₃)₅ - the first supramolecular ozonide compound^[11]

The reaction of [12]crown-4 with CsO3 in liquid ammonia yields this compound. Left: The prominent structural feature are 1∞{Cs8(O3)10}2- rods which are arranged in a tetragonal rod packing (see below).

The structural confinement enforced by the small crown ether molecules lead to remarkably short intermolecular O⋅⋅⋅O distances indicated by the dotted red line in the figure above.

A recent review:

• M. Jansen, H. Nuss: Z. Anorg. Allg. Chem. 2007, 633, 1307.

References:

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• W. Hesse, M. Jansen, W. Schnick: Prog. Solid St. Chem. 1989, 19, 47.
• W. Hesse, M. Jansen: Inorg. Chem. 1991, 30, 4380.
• N. Korber, M. Jansen: Chem. Ber. 1992, 125, 1383.
• W.Klein, M. Jansen: Z. Anorg. Allg. Chem. 2000, 626, 947.
• W. Klein, M. Jansen: Z. Naturforsch. 2005, 60b, 426.
• W. Assenmacher, M. Jansen: Z. Anorg. Allg. Chem. 1995, 621, 431.
• H. Seyeda, K. Armbruster, M. Jansen: Chem. Ber. 1996, 129, 997.
• P. D. C. Dietzel, M. Jansen: Z. Anorg. Allg.Chem. 2006, 632, 2276.
• N. Korber, M. Jansen: J. Chem. Soc., Chem. Commun. 1990, 1654.
• H. Nuss, M. Jansen: Angew. Chem. Int. Ed. 2006,45, 7969.
• H. Nuss, J. Nuss, M. Jansen: Z. Anorg. Allg. Chem. 2008, 634, 1291.
• H. Nuss, M. Jansen: Z. Naturforsch. 2009, 64b, 1325.