For a long time, Zintl ions of Group 14 and 15 elements were considered to be remarkable species domiciled in solid-state chemistry that have unexpected stoichiometries and fascinating structures, but were of limited relevance. The revival of Zintl ions was heralded by the observation that these species, preformed in solid-state Zintl phases, can be extracted from the lattice of the solids and dissolved in appropriate solvents, and thus become available as reactants and building blocks in solution chemistry. The recent upsurge of research activity in this fast-growing field has now provided a rich plethora of new compounds, for example by substitution of these Zintl ions with organic groups and organometallic fragments, by oxidative coupling reactions leading to dimers, oligomers, or polymers, or by the inclusion of metal atoms under formation of endohedral cluster species and intermetalloid compounds; some of these species have good prospects in applications in materials science. This Review presents the enormous progress that has been made in Zintl ion chemistry with an emphasis on syntheses, properties, structures, and theoretical treatments.

Highest possible symmetry! Nine Sn atoms are arranged to give an almost perfect sphere around a Cu atom in the endohedrally filled Zintl ion [Cu@Sn9]3−. The rapid equilibration of the nine Sn atoms on the spectral NMR timescale leads to an exceptionally sharp 63Cu NMR signal. In contrast to the more common endohedrally filled fullerenes, the title complexes can be synthesized in macroscopic quantities as [K([2.2.2]crypt)]+ salts.

The endohedral stannaspherene cluster anion [Ir@Sn(12)](3-) was synthesized in two steps. The reaction of K(4)Sn(9) with [IrCl(cod)](2) (cod: 1,5-cyclooctadienyl) in ethylenediamine (en) solution first yielded the [K(2,2,2-crypt)](+) salt (2,2,2-crypt: 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) of the capped cluster anion [Sn(9)Ir(cod)](3-). Subsequently, crystals of this compound were dissolved in en, followed by the addition of triphenylphosphine or 1,2-bis(diphenylphosphino)ethane and treatment at elevated temperatures. [Ir@Sn(12)](3-) was obtained and characterized as the [K(2,2,2-crypt)](+) salt. The isolation of [Sn(9)Ir(cod)](3-) as an intermediate product establishes that the formation of the stannaspherene [Ir@Sn(12)](3-) occurs through the oxidation of [Sn(9)Ir(cod)](3-). Among the structurally characterized tetrel cluster anions, [Ir@Sn(12)](3-) is a unique example of a stannaspherene, and one of the rare spherical clusters encapsulating a metal atom that is not a member of Group 10. Single-crystal structure determination shows that the novel Zintl ion cluster has nearly perfect icosahedral I(h) point symmetry.

The synthesis and crystal structure of the first ternary A-Cu-Sn intermetallic phases for the heavier alkali metals A = Na to Cs is reported. The title compounds A(12)Cu(12)Sn(21) show discrete 33-atom intermetalloid Cu-Sn clusters {Sn@Cu(12)@Sn(20)}, which are composed of {Sn(20)} pentagonal dodecahedra surrounding {Cu(12)} icosahedra with single Sn atoms at the center. Na(12)Cu(12)Sn(21) and K(12)Cu(12)Sn(21) were characterized by single-crystal XRD studies, and the successful synthesis of analogous A-Cu-Sn compounds with A = Rb and Cs is deduced from powder XRD data. The isotypic A(12)Cu(12)Sn(21) phases crystallize in the cubic space group Pn ̅3m (No. 224), with the Cu-Sn clusters adopting a face centered cubic arrangement. A formal charge of 12- can be assigned to the {Sn@Cu(12)@Sn(20)} cluster unit, and the interpretation of the title compounds as salt-like intermetallic phases featuring discrete anionic intermetalloid [Sn@Cu(12)@Sn(20)](12-) clusters separated by alkali metal cations is supported by electronic structure calculations. For both Na(12)Cu(12)Sn(21) and K(12)Cu(12)Sn(21), DFT band structure calculations (TB-LMTO-ASA) reveal a band gap. The discrete [Sn@Cu(12)@Sn(20)](12-) cluster is analyzed in consideration of the molecular orbitals obtained from hybrid DFT calculations (Gaussian 09) for the cluster anion. The [Sn@Cu(12)@Sn(20)](12-) cluster MOs can be classified with labels indicating the numbers of radial and angular nodes, in the style of spherical shell models of cluster bonding.

Inorganic pentaprismane: The unusual structure of the anion [Co@Ge(10)](3-), which was obtained by the reaction of K(4)Ge(9) with [Co(C(8)H(12))(C(8)H(13))] in ethylenediamine, raises questions about chemical bonding in the anion. The Zintl ion cluster has virtual D(5h) symmetry and is a unique example of a ligand-free cluster that is not a deltahedron. The delocalized chemical bonding is represented in the picture by one of the bonding orbitals of the anion.