Derivatization of deltahedral Zintl ions by nucleophilic addition: [Ph-Ge9-SbPh2]2- and [Ph2Sb-Ge9-Ge9-SbPh2]4-

The type of the reactions of addition of exo-bonded groups to deltahedral Zintl ions such as Ge9(n-) has been established as addition of anionic nucleophiles. Various nucleophiles such as Ph2Bi-, Ph2Sb-, Ph- interact with the relatively low-lying LUMO of Ge9(2-) and/or the half filled HOMO of Ge9(3-) and bond to the clusters. The title anions, characterized in their (K-crypt) salts where crypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-[8.8.8]-hexacosane, and the previously characterized [Ph2Sb-Ge9-SbPh2](2-) are made by a reaction of K4Ge9 with SbPh3 in ethylenediamine. [Ph-Ge9-SbPh2](2-) is the first ogranically functionalized deltahedral Zintl ion, i.e., a deltahedral ion with a direct carbon-cluster covalent bond, that can exists without the substituents as well. The Ge(9) clusters resemble tricapped trigonal prisms with one elongated edge (one of the three edges parallel to the pseudo 3-fold axis). The two substituents are always bonded to the vertexes of such an elongated edge. The same is true for the intercluster bond in [Ph2Sb-Ge9-Ge9-SbPh2)](4-).     

Tin-based organo-Zintl ions: alkylation and alkenylation of Sn9(4-)

Reactions of nine-atom deltahedral clusters (Zintl ions) of tin, Sn 9 (4-), with alkyl chlorides, RCl (R = (t) Bu, (n) Bu, (s) Bu), and alkynes (Me3Si-C[triple bond]C-SiMe3, Ph-C[triple bond]CH) yielded the corresponding alkylated and alkenylated clusters [Sn 9-R] (3-). The triple bonds of the alkynes are hydrogenated to double bonds in the process. These are the first tin-based organo-Zintl ions, that is Zintl ions of tin that were subsequently functionalized with organic groups. They are analogous to the recently reported germanium-based derivatives. The (t) Bu-, vinyl-, and styrene-functionalized clusters [Sn 9- (t) Bu] (3-), [Sn 9-CH=CH 2] (3-), and [Sn 9-CH=CH-Ph] (3-), respectively, were structurally characterized in the solid state with [K(2,2,2-crypt)] (+) countercations and in solution by electrospray mass spectrometry. Crystal data: [K(2,2,2-crypt)] 3[Sn 9- (t) Bu].2py, triclinic, P1, a = 14.4259(3), b = 16.2725(4), and c = 22.5593(5) A, alpha = 86.092(1), beta = 78.952(1), and gamma = 65.114(1) degrees , V = 4714.48(7) A (3), Z = 2; [K(2,2,2-crypt)] 3[Sn 9-CH=CH 2].2py, triclinic, P-1, a = 15.6988(3), b = 17.4195(4), and c = 17.4432(4) A, alpha = 86.299(1), beta = 81.566(1), and gamma = 85.349(1) degrees , V = 4696.27(18) A (3), Z = 2; [K(2,2,2-crypt)] 3[Sn 9-CH=CH-Ph].tol.0.75py, monoclinic, C2/c, a = 38.5883(9), b = 23.3893(5), and c = 25.0192(5) A, beta = 120.269(1) degrees , V = 19502.6(7) A (3), Z = 8.     

Rationally functionalized deltahedral zintl ions: synthesis and characterization of [Ge9-ER3]3-, [R3E-Ge9-ER3]2-, and [R3E-Ge9-Ge9-ER3]4- (E=Ge, Sn; R=Me, Ph)

Six new derivatized deltahedral Zintl ions have been synthesized by reactions between the known Zintl ions Ge(9) (n-) with the halides R(3)EX and/or the corresponding anions R(3)E(-) for E=Ge or Sn. This rational approach is based on our previous discovery that these derivatization reactions are based on nucleophilic addition to the clusters. All species were structurally characterized as their salts with potassium countercations sequestered in 2,2,2-crypt or [18]crown-6 ether. The tin-containing anions were characterized also in solutions by (119)Sn NMR spectroscopy. The reaction types for such substitutions and the structures of the new anions are discussed.     

Rational synthesis of [Ge9{Si(SiMe3)3}3]- from its parent Zintl ion Ge9(4-)

Reported is the first rational synthesis of a trisubstituted deltahedral Zintl ion, [Ge(9){Si(SiMe(3))(3)}(3)](-) in this case, by the addition of the three substituents in a reaction of the parent naked deltahedral Zintl ion Ge(9)(4-) with {(Me(3)Si)(3)Si}Cl. The new species were crystallized and structurally characterized in [K(2,2,2-crypt)](2)[Ge(9){Si(SiMe(3))(3)}(3)] (monoclinic, P2(1)/c, a = 26.497(3) ?, b = 24.090(2) ?, c = 29.268(3) ?, β = 113.888(2)°, V = 17082(3) ?(3), Z = 8, R1/wR2 = 0.0436/0.0812 for the observed data and 0.1023/0.1010 for all data).     

Ph(2)Bi-(Ge(9))-BiPh(2)](2-): a deltahedral Zintl ion functionalized by exo-bonded ligands

The title anion was synthesized by a reaction of nido-Ge(9)(4-), made from K(4)Ge(9) dissolved in ethylenediamine and 2,2,2-crypt(4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane), with BiPh(3). It was structurally characterized in (K-2,2,2-crypt)(2)[Ge(9)(BiPh(2))(2)].en which was crystallized from the solution. The anion is a monocapped square antiprism of Ge(9) with two diphenylbismuth ligands exo-bonded to opposite vertexes of the open face of the cluster. This is the first example where covalently exo-bonded ligands are attached to a deltahedral cluster that can exist without them as well.     

Heteroatomic deltahedral clusters: synthesis and structures of closo-[Bi3Ni(4)(CO)6]3-, closo-[Bi4Ni4(CO)6]2-, the open cluster [Bi3Ni6(CO)9]3-, and the intermetalloid closo-[Nix@[Bi6Ni6(CO)8)]4-

Reactions of ethylenediamine solutions of K4Bi5 with Ni(PPh3)2(CO)2 yielded four novel hetero-atomic Bi/Ni deltahedral clusters. Three of them, the 7-atom pentagonal bipyramidal [Bi3Ni4(CO)6]3-, the 8-atom dodecahedral [Bi4Ni4(CO)6]2-, and the Ni-centered or empty 12-atom icosahedral [Nix@[Bi6Ni6(CO)8]4-, are closo-species according to both electron count and shape. The centered icosahedral cluster resembles packing in intermetallic compounds and belongs to the emerging class of intermetalloid clusters. The shape of the fourth cluster, [Bi3Ni6(CO)9]3-, can be derived from the icosahedral Ni-centered [Ni@[Bi6Ni6(CO)8]4- by removal of three Bi- and one Ni-atoms of two neighboring triangular faces. The clusters were structurally characterized by single-crystal X-ray diffraction in compounds with potassium cations sequestered by 2,2,2-crypt or 18-crown-6 ether. They were also characterized in solution by electrospray mass spectrometry.     

Ge(9)=Ge(9)=Ge(9)](6-): a linear trimer of 27 germanium atoms

The title anion was synthesized by oxidation of nido-Ge94- with Ph3P or Ph3As in ethylenediamine solution. It was structurally characterized in the compound (Rb-2,2,2-crypt)6[Ge9=Ge9=Ge9].3en (2,2,2-crypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) crystallized from the solution. The anion is a linear trimer of nine-atom clusters with the shape of tricapped trigonal prisms elongated along two of the three prismatic edges. Each pair of clusters is connected by two exo-bonds.     

Metal-centered deltahedral Zintl ions: synthesis of [Ni@Sn9]4- by direct extraction from intermetallic precursors and of the vertex-fused dimer [{Ni@Sn8(μ-Ge)(1/2)}2]4-

Ni-centered deltahedral Sn(9) clusters with a charge of 4-, i.e., [Ni@Sn(9)](4-), were extracted in ethylenediamine in high yield directly from intermetallic precursors with the nominal composition "K(4)Sn(9)Ni(3)". The new endohedral clusters were crystallized and structurally characterized in K[K(18-crown-6)](3)[Ni@Sn(9)]·3benzene (1a, triclinic, P1?, a = 10.2754(5) ?, b = 19.5442(9) ?, and c = 20.5576(13) ?, α = 73.927(3)°, β = 79.838(4)°, and γ = 84.389(3)°, V = 3899.6(4) ?(3), Z = 2) and K[K(2,2,2-crypt)](3)[Ni@Sn(9)] (1b, triclinic, P1, a = 15.8028(8) ?, b = 16.21350(9) ?, and c = 20.1760(12) ?, α = 98.71040(10)°, β = 104.4690(10)°, and γ = 118.3890(10)°, V = 4181.5(4) ?(3), Z = 2). The alternative method of a post-synthetic insertion of a Ni atom in empty Sn(9) clusters by a reaction with Ni(cod)(2) predominantly produces the more-oxidized clusters with a charge of 3-, i.e., the recently reported [Ni@Sn(9)](3-). Nonetheless, using substoichiometric amounts of 18-crown-6 as a cation sequestering agent, we also have been able to isolate the 4- clusters as a minor phase from such reactions. They were structurally characterized in K[K(en)][K(18-crown-6)](2)[Ni@Sn(9)]·0.5en (2, monoclinic, P2(1)/n, a = 10.4153(5) ?, b = 25.6788(11) ?, and c = 20.6630(9) ?, β = 102.530(2)°, V = 5394.7(4) ?(3), Z = 2). The ability of the Ni-centered clusters to exist with both 3- and 4- charges parallels the same ability of the empty clusters and is very promising for similarly rich chemistry involving electron transfer and flexible "oxidation states". We also report the synthesis and characterization of the endohedral heteroatomic dimer [{Ni@Sn(8)(μ-Ge)(1/2)}(2)](4-) composed of two [Ni@(Sn(8)Ge)]-clusters fused at the Ge-vertex. The dimer was synthesized by reacting an ethylenediamine solution of a ternary precursor with the nominal composition "K(4)Ge(4.5)Sn(4.5)", which is known to produce heteroatomic Ge(9-x)Sn(x) clusters, with Ni(cod)(2). It is isostructural with the reported [{Ni@Sn(8)(μ-Sn)(1/2)}(2)](4-) and is structurally characterized in [K-(2,2,2-crypt)](4)[{Ni@Sn(8)(μ-Ge)(1/2)}(2)]·2en (3, monoclinic, C2/c, a = 30.636(2) ?, b = 16.5548(12) ?, and c = 28.872(2) ?, β = 121.2140(10)°, V = 12523.5(15) ?(3), Z = 4).     

Ge9=Ge9=Ge9=Ge9]8-: a linear tetramer of nine-atom germanium clusters,a nanorod

A tetramer of nine-atom deltahedral germanium clusters and charge 8-, [Ge9=Ge9=Ge9=Ge9]8- , has been characterized as a (Rb-18C6)(+) salt (18C6 = 18-crown-6 polyether). The clusters are connected by pairs of parallel bonds, and the electrons are delocalized over the whole anion. The size of the tetramer is of nanorod dimensions, ca. 2 nm.     

Ligand-free deltahedral clusters of silicon in solution: synthesis, structure, and electrochemistry of Si9(2-)

Deltahedral nine-atom clusters of silicon, Si(9)(2-), were synthesized by mild oxidation of a liquid ammonia solution of K(12)Si(17) with Ph(3)GeCl in the presence of 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) or 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane). The clusters were structurally characterized in [K(18-crown-6)](2)Si(9).C(5)H(5)N (yellow; orthorhombic, Pnma; a = 14.013(1), b = 18.108 (1), c = 18.320 (1) A; Z = 4) crystallized from a pyridine solution of the product of the aforementioned reaction in liquid ammonia. Si(9)(2-) is the first unequivocally characterized nine-atom cluster of group 14 with a charge of 2-. In addition to pyridine, the product from the reaction in liquid ammonia is also soluble in DMF, and the Si(9)(2-) clusters were characterized by mass spectrometry in such a solution. The more reduced clusters Si(9)(3-) have also been crystallized from pyridine solution. Cyclic voltammetry in both pyridine and DMF solutions clearly shows the Si(9)(2-)/Si(9)(3-) redox couple as one-electron reversible process. The structural similarities and differences between Si(9)(3-) and Si(9)(2-) are discussed herein.     

Deltahedral germanium clusters: insertion of transition-metal atoms and addition of organometallic fragments

Reactions of nine-atom deltahedral clusters of germanium with Ni(COD)2 and/or Ni(PPh3)2(CO)2 in ethylenediamine yielded the Ni-centered heteroatomic 10-atom clusters [Ni@(Ge9Ni-CO)]2- and [Ni@(Ge9Ni-en)]3-, as well as the empty 10-atom heteroatomic cluster [Ge9Ni-CO]3-. A ligand exchange reaction between [Ni@(Ge9Ni-CO)]2- and potassium phenylacetylide produced the organically functionalized species [Ni@(Ge9Ni-CCPh)]3-. The empty cluster [Ge9Ni-CO]3- is a bicapped square antiprism where one of the capping vertexes is the nickel atom. The other three clusters are tricapped trigonal prisms where an additional 10th vertex of monoligated nickel caps a triangular base of the trigonal prism. As a result of this, that base opens up, and the distances within it become nonbonding. This ensures that all atoms of the cluster are equidistant from the central nickel atom, i.e., the cluster is very close to spherical. All species were structurally characterized in crystalline compounds with [K-(2,2,2-crypt)]+ countercations. They were also characterized in solution by mass spectrometry, IR, and 13C NMR.     

"n-Doping" of deltahedral Zintl ions

We report a simple and efficient method for replacing germanium atoms in deltahedral Ge(9)(4-) clusters with Sb or Bi. While reactions of Ge(9)(4-) with EPh(3) (E = Sb, Bi) at room temperature are known to produce mono- and disubstituted clusters [Ph(2)E-Ge(9)-Ge(9)-EPh(2)](4-) and [Ph(2)E-Ge(9)-EPh(2)](2-), respectively, at elevated temperatures or with sonication they result in exchange of Ge cluster atoms with Sb or Bi. Structurally characterized from such reactions are the novel "n-doped" deltahedral Zintl ions [(EGe(8))-(Ge(8)E)](4-), (Sb(2)Ge(7))(2-), and [(SbGe(8))-SbPh(2)](2-).     

The Pb12(2-) and Pb10(2-) zintl ions and the M@Pb12(2-) and M@Pb10(2-) cluster series where M = Ni, Pd, Pt

Ethylenediamine (en) solutions of K4Pb9 react with toluene solutions of ML4 (M = Pt, Pd, L = PPh3; M = Ni, L2= COD) and 2,2,2-crypt to give M@Pb12(2-) cluster anions (M = Pt (1), Pd (2), Ni (3)) as the [K(2,2,2-crypt)]+ salts in low (Ni) to good (Pt) yields. The ions have near perfect Ih point symmetry and have been characterized by X-ray diffraction, 207Pb NMR and LDI-TOF mass spectrometry studies. For M = Ni, the primary product formed is the D4d Ni@Pb10(2-) cluster that has also been structurally characterized. The M@Pb10(2-) clusters (M = Pd, Pt) and the new Zintl ions closo-Pb10(2-) and closo-Pb12(2-) were formed in the gas phase but have not been detected in solution or the solid state. The structural trends of these series of clusters have been investigated through DFT calculations. The Ni@Pb10(2-) cluster is dynamic on the 207Pb NMR time scale at -45 degrees C and 104.7 MHz. The M@Pb12(2-) ions show unusually deshielded 207Pb NMR chemical shifts that presumably arise from sigma-aromatic effects associated with their high symmetries. In the solid state, the salts form superlattices of cations and anions (e.g. the AlB2 lattice of [K(2,2,2-crypt)](2)[Pt@Pb12]) and are prototypes for "assembled cluster materials".     

The Zintl ion [As7]2-: an example of an electron-deficient As(x) radical anion

[K(2,2,2-crypt)](2)[As(7)]·THF, 1 (2,2,2-crypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) is the first well characterized seven-atom radical anion of group 15. UV-Vis spectroscopy confirms the presence and electronic structure of [As(7)](2-). Cyclic voltammetry in DMF solution shows the As(7)(3-)/As(7)(2-) redox couple as a one-electron reversible process. Theoretical investigations explore the bonding and properties of compound 1.     

Synthesis, Structure, and Reactivities of [eta(2)-P(7)M(CO)(4)](3)(-), [eta(2)-HP(7)M(CO)(4)](2)(-), and [eta(2)-RP(7)M(CO)(4)](2)(-) Zintl Ion Complexes Where M = Mo, W

Ethylenediamine (en) solutions of [eta(4)-P(7)M(CO)(3)](3)(-) ions [M = W (1a), Mo (1b)] react under one atmosphere of CO to form microcrystalline yellow powders of [eta(2)-P(7)M(CO)(4)](3)(-) complexes [M = W (4a), Mo (4b)]. Compounds 4 are unstable, losing CO to re-form 1, but are highly nucleophilic and basic. They are protonated with methanol in en solvent giving [eta(2)-HP(7)M(CO)(4)](2)(-) ions (5) and are alkylated with R(4)N(+) salts in en solutions to give [eta(2)-RP(7)M(CO)(4)](2)(-) complexes (6) in good yields (R = alkyl). Compounds 5 and 6 can also be prepared by carbonylations of the [eta(4)-HP(7)M(CO)(3)](2)(-) (3) and [eta(4)-RP(7)M(CO)(3)](2)(-) (2) precursors, respectively. The carbonylations of 1-3 to form 4-6 require a change from eta(4)- to eta(2)-coordination of the P(7) cages in order to maintain 18-electron configurations at the metal centers. Comparative protonation/deprotonation studies show 4 to be more basic than 1. The compounds were characterized by IR and (1)H, (13)C, and (31)P NMR spectroscopic studies and microanalysis where appropriate. The [K(2,2,2-crypt)](+) salts of 5 were characterized by single crystal X-ray diffraction. For 5, the M-P bonds are very long (2.71(1) ?, average). The P(7)(3)(-) cages of 5 are not displaced by dppe. The P(7) cages in 4-6 have nortricyclane-like structures in contrast to the norbornadiene-type geometries observed for 1-3. (31)P NMR spectroscopic studies for 5-6 show C(1) symmetry in solution (seven inequivalent phosphorus nuclei), consistent with the structural studies for 5, and C(s)() symmetry for 4 (five phosphorus nuclei in a 2:2:1:1:1 ratio). Crystallographic data for [K(2,2,2-crypt)](2)[eta(2)-HP(7)W(CO)(4)].en: monoclinic, space group C2/c, a = 23.067(20) ?, b = 12.6931(13) ?, c = 21.433(2) ?, beta = 90.758(7) degrees, V = 6274.9(10) ?(3), Z = 4, R(F) = 0.0573, R(w)(F(2)) = 0.1409. For [K(2,2,2-crypt)](2)[eta(2)-HP(7)Mo(CO)(4)].en: monoclinic, space group C2/c, a = 22.848(2) ?, b = 12.528(2) ?, c = 21.460(2) ?, beta = 91.412(12) degrees, V = 6140.9(12) ?(3), Z = 4, R(F) = 0.0681, R(w)(F(2)) = 0.1399.     

A highly distorted open-shell endohedral Zintl cluster: [Mn@Pb12]3-

Reaction of an ethylenediamine (en) solution of K(4)Pb(9) and 2,2,2-crypt (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) with a tetrahydrofuran (THF) solution of Mn(3)(Mes)(6) (Mes = 2,4,6-trimethylphenyl) yielded the anionic cluster [Mn@Pb(12)](3-). This species was observed in the positive and negative ion-mode electrospray mass-spectra of the crude reaction mixture. The crystalline samples obtained from such solutions allowed us to confirm the composition of the sample as [K(2,2,2-crypt)](3)[Mn@Pb(12)]·1.5en (1). Because of numerous issues related to crystal sample quality and crystallographic disorder a high-quality crystal structure solution could not be obtained. Despite this, however, the data collected permit us to draw reasonable conclusions about the charge and connectivity of the [Mn@Pb(12)](3-) cluster anion. Crystals of 1 were further characterized by elemental analysis and electron paramagnetic resonance (EPR). Density Functional Theory (DFT) calculations on such a system reveal a highly distorted endohedral cluster anion, consistent with the structural distortions observed by single crystal X-ray diffraction. The cluster anions are considerably expanded compared to the 36-electron closed-shell analogue [Ni@Pb(12)](2-) and, moreover, exhibit significant low-symmetry distortions from the idealized icosahedral (I(h)) geometry that is characteristic of related endohedral clusters. Our computations indicate that there is substantial transfer of electron density from the formally Mn(-I) center to the low-lying vacant orbitals of the [Pb(12)](2-) cage.     

Heteroatomic deltahedral clusters of main-group elements: synthesis and structure of the Zintl ions [In4Bi5]3-, [InBi3]2-, and [GaBi3]2-

Reported are the first heteroatomic deltahedral Zintl ions made of elements differing by more than one group, indium or gallium and bismuth. Nine-atom clusters [In4Bi5]3- are characterized in two different compounds, (Na-crypt)3[In4Bi5] (4, P2(1)/n, a = 23.572(6) A, b = 15.042(4) A, c = 24.071(4) A, beta = 106.00(3) degrees, Z = 4) and (K-crypt)6[In4Bi5][In4Bi5].1.5en.0.5tol (5, P2(1)/c, a = 28.532(2) A, b = 23.707(2) A, c = 28.021(2) A, beta = 93.274(4) degrees, Z = 4). Tetrahedra of [InBi3]2- or [GaBi3]2- are found in (K-crypt)2[InBi3].en (1, P2(1), a = 12.347(4) A, b = 20.884(4) A, c = 12.619(7) A, beta = 119.02(4) degrees, Z = 2) and in the isostructural (Rb-crypt)2[InBi3].en (2, a = 12.403(8) A, b = 20.99(1) A, c = 12.617(9) A, beta = 118.83(4) degrees) and (K-crypt)2[GaBi3].en (3, a = 12.324(5) A, b = 20.890(8) A, c = 12.629(5) A, beta = 118.91(3) degrees). All compounds are crystallized from ethylenediamine/crypt solutions of precursors with nominal composition "A5E2Bi4" where A = Na, K, or Rb and E = Ga or In. The cluster in 4 is a well-ordered monocapped square antiprism with the four indium atoms occupying the five-bonded positions. Compound 5 contains two independent [In4Bi5]3- clusters; one is the same as the cluster in 4, while the other is a tricapped trigonal prism with two elongated prismatic edges. All compounds are EPR-silent and therefore diamagnetic.     

Syntheses; 77Se, 203Tl, and 205Tl NMR; and theoretical studies of the Tl2Se6(6-), Tl3Se6(5-), and Tl3Se7(5-) anions and the X-ray crystal structures of [2,2,2-crypt-Na]4[Tl4Se8].en and [2,2,2-crypt-Na]2[Tl2Se4](infinity)1.en

The 2,2,2-crypt salts of the Tl4Se8(4-) and [Tl2Se4(2-)]infinity1 anions have been obtained by extraction of the ternary alloy NaTl0.5Se in ethylenediamine (en) in the presence of 2,2,2-crypt and 18-crown-6 followed by vapor-phase diffusion of THF into the en extract. The [2,2,2-crypt-Na]4[Tl4Se8].en crystallizes in the monoclinic space group P2(1)/n, with Z = 2 and a = 14.768(3) angstroms, b = 16.635(3) angstroms, c = 21.254(4) angstroms, beta = 94.17(3) degrees at -123 degrees C, and the [2,2,2-crypt-Na]2[Tl2Se4]infinity1.en crystallizes in the monoclinic space group P2(1)/c, with Z = 4 and a = 14.246(2) angstroms, b = 14.360(3) angstroms, c = 26.673(8) angstroms, beta = 99.87(3) degrees at -123 degrees C. The TlIII anions, Tl2Se6(6-) and Tl3Se7(5-), and the mixed oxidation state TlI/TlIII anion, Tl3Se6(5-), have been obtained by extraction of NaTl0.5Se and NaTlSe in en, in the presence of 2,2,2-crypt and/or in liquid NH3, and have been characterized in solution by low-temperature 77Se, 203Tl, and 205Tl NMR spectroscopy. The 1J(203,205Tl-77Se) and 2J(203,205Tl-203,205Tl) couplings of the three anions have been used to arrive at their solution structures by detailed analyses and simulations of all spin multiplets that comprise the 205,203Tl NMR subspectra arising from natural abundance 205,203Tl and 77Se isotopomer distributions. The structure of Tl2Se6(6-) is based on a Tl2Se2 ring in which each thallium is bonded to two exo-selenium atoms so that these thalliums are four-coordinate and possess a formal oxidation state of +3. The Tl4Se8(4-) anion is formally derived from the Tl2Se6(6-) anion by coordination of each pair of terminal Se atoms to the TlIII atom of a TlSe+ cation. The structure of the [Tl2Se4(2-)]infinity1 anion is comprised of edge-sharing distorted TlSe4 tetrahedra that form infinite, one-dimensional [Tl2Se42-]infinity1 chains. The structures of Tl3Se6(5-) and Tl3Se7(5-) are derived from Tl4Se4-cubes in which one thallium atom has been removed and two and three exo-selenium atoms are bonded to thallium atoms, respectively, so that each is four-coordinate and possesses a formal oxidation state of +3 with the remaining three-coordinate thallium atom in the +1 oxidation state. Quantum mechanical calculations at the MP2 level of theory show that the Tl2Se6(6-), Tl3Se6(5-), Tl3Se7(5-), and Tl4Se8(4-) anions exhibit true minima and display geometries that are in agreement with their experimental structures. Natural bond orbital and electron localization function analyses were utilized in describing the bonding in the present and previously published Tl/Se anions, and showed that the Tl2Se6(6-), Tl3Se6(5-), Tl3Se7(5-), and Tl4Se8(4-) anions are electron-precise rings and cages.     

Synthesis and structure of [K(+)-(2,2)diaza-[18]-crown-6][K3Ge9]-2ethylenediamine: stabilization of the two-dimensional layer (2)(infinity)[K3Ge9(1-)

Large bright-red, transparent crystalline plates of [K-(2,2)diaza-[18]-crown-6]K3Ge9-2en are obtained, in high-yield, from a reaction of (2,2)diaza-[18]-crown-6 in toluene with a solution of K4Ge9/potassium metal (K) in ethylenediamine (en). The compound crystallizes in the monoclinic space group P2(1)/m (a = 10.740(1) A, b = 15.812(1) A, c = 12.326(1) A, beta = 114.74 degrees; Z = 2). The crystal structure of [K-(2,2)diaza-[18]-crown-6]K3Ge9-2en features two-dimensional [K3Ge9] layers formed by uncomplexed K(+) cations and Ge94(-) anions. The "not-so-bare" cluster compound features a unique Ge94(-) cluster that exhibits a slightly distorted C(2v) geometry that is closer to D(3h) than the expected C(4v). Use of noncryptand sequestering agents in the isolation of Ge cluster anions from en solutions opens new avenues in understanding important cation-anion interactions in the stability and reactivity of Zintl ions, as well as a viable route to isolating Zintl anions with higher charges per atom.     

A versatile salt-metathesis route to heteroatomic clusters derived from phosphorus and arsenic Zintl anions

Salt metathesis reactions between ethylenediamine (en) solutions of the K(3)E(7) (E = P, As) Zintl phases and post-transition metal halides (InCl(3), TlCl, SnI(2) and PbI(2)) have yielded a family of novel heteroatomic cluster anions, [In(E(7))(2)](3-), [TlE(7)](2-) and [E'E(15)](3-) (E' = Sn, Pb; E = P, As). Several of these new species have been characterized by single-crystal X-ray diffraction as salts of sequestered potassium cations in [K(2,2,2-crypt)](3)[In(P(7))(2)]·3.5py (1), [K(2,2,2-crypt)](2)[TlP(7)]·py (3), [K(18-crown-6)](2)[TlAs(7)] (4b), [K(2,2,2-crypt)](3)[E'P(15)]·en (E' = Sn (5), Pb (6)) and [K(2,2,2-crypt)](3)[SnAs(15)]·2en (7). The presence of all of the cluster anions in solution was confirmed by electrospray mass-spectrometry and by (1)H and (31)P{(1)H} NMR spectroscopy when pertinent.