A Bowl-Type Dodecavanadate as a Halide Receptor.

The dodecavanadate framework, [V12O32]4-, exhibits a unique bowl-type structure with an open molecular oxide cage having a cavity diameter of 4.4 Å, and different synthetic paths were required to construct the bowl-type structure with a different guest. A new dodecavanadate, {(n-C4H9)4N}4[V12O32(CH3NO2)] (1), is synthesized with a nitromethane guest, which is stacked above the entrance of the hemisphere rather than fully occupying the cavity, and it enables a guest-capturing reaction, while retaining the anionic cage structure. Compound 1 is a good precursor for halide-centered dodecavanadates, {(C2H5)4N}5[V12O32(X)] (X = Cl- (2), Br- (3), and I- (4)). The position of the halide inside the cavity correlates with the ionic radius of the guest; the small chloride ion sat at the far bottom, and the large iodide floated at the entrance. The inclusion reaction rates were estimated through 51V NMR time-course measurements in nitromethane. The reaction rates increase in the order I- < Br- < Cl-.

Decatantalate--the last member of the group 5 decametalate family.

A tetra-n-butylammonium (TBA) salt of [Ta10O28](6-) was synthesized by heating TBA6[H2Ta6O19] in toluene for a prolonged period. X-ray structural analysis of TBA6[Ta10O28]·6H2O revealed that the anion has the decametalate structure and is isostructural with the decavanadate and decaniobate anions [a = 15.8517(8) Å, b = 19.364(1) Å, c = 21.935(1) Å, ß = 93.638(1)°, V = 6719.4(6) Å(3), Z = 2, and space group P2(1)/n at 292(2) K].

Long hydrogen-bonded rod of molecular oxide: a hexatantalate tetramer.

A tetra-n-butylammonium (TBA) salt of [H(4.5)(Ta(6)O(19))](3.5-) was synthesized by reacting hydrous tantalum oxide with TBAOH. X-ray structural analysis of TBA(3.5)[H(4.5)(Ta(6)O(19))]·2THF·5.5H(2)O (THF = tetrahydrofuran) revealed that this compound consists of a hydrogen-bonded, rod-shaped tetramer of hexatantalate that is almost 30 Å long together with TBA cations and solvent molecules of crystallization [a = 20.6354(5) Å, b = 25.5951(7) Å, c = 37.2058(8) Å, α = 77.092(1)°, ß = 86.177(1)°, γ = 88.683(1)°, V = 19110.9(8) Å(3), Z = 8, and space group P ̅1]. (1)H NMR spectra showed that this tetrameric structure is maintained in solution.

[H(x)TeV9O28]((5-x)-) (x=1 and 2): vanadotellurates with decavanadate structure.

Two new vanadotellurates, [HTeV(9)O(28)](4-) and [H(2)TeV(9)O(28)](3-) have been synthesized and structurally characterized as tetra-n-butylammonium (TBA) salts: TBA(4)[HTeV(9)O(28)]·2CH(3)CN [triclinic, space group P ̅1, a = 16.7102(6) Å, b = 17.4680(7) Å, c = 17.9634(7) Å, α = 74.412(1)°, ß = 67.494(1)°, γ = 74.160(2)°, Z = 2] and TBA(3)[H(2)TeV(9)O(28)] [monoclinic, space group P2(1)/c, a = 13.0013(5) Å, b = 19.157(1) Å, c = 28.453(1) Å, ß = 97.222(2)°, Z = 4]. The results of the structural analyses indicate that the four O atoms that bridge two V atoms on the Te side are the most basic ones in the structure. The results of density-functional theory (DFT) calculations support this view.

Methylated molybdoplatinate--its unexpected ability to absorb methanol.

Methylated molybdoplatinate of the Anderson structure was obtained as a tetra-n-butylammonium (TBA) salt by reacting MoO(3), H(2)Pt(OH)(6), and aqueous TBAOH in a 6 : 1 : 4 ratio, which absorbed huge amounts of MeOH, more than three times as much as its own weight.

Tetrahedral tellurate.

A tetraethylammonium (TEA) salt of TeO 4 (2-) was synthesized by reacting Te(OH) 6 with tetraethylammonium hydroxide. X-ray structural analysis of (TEA) 2TeO 4.2H 2O confirmed that this new compound consists of discrete TeO 4 (2-) anions of distorted tetrahedral structure together with TEA cations and water molecules of crystallization [ a = 8.0820(9) A, b = 13.7730(12) A, c = 20.1590(18) A, V = 2244.0(4) A (3), Z = 4, and space group Pccb]. The (125)Te NMR spectrum indicated that water reacts with the TeO 4 (2-) anion to regenerate octahedral tellurate species in solution.

Protonation and methylation of an Anderson-type polyoxoanion [IMo6O24]5-.

A series of protonated and methylated Anderson-type molybdoperiodates as well as the unprotonated [IMo6O24]5- have been synthesized and structurally characterized as tetra-n-butylammonium salts: [(n-C4H9)4N]5[IMo6O24] [monoclinic, space group C2/c, a = 33.6101(3) A, b = 15.2575(1) A, c = 24.0294(2) A, beta = 126.9569(3) degrees , Z = 4], [(n-C4H9)4N]4[IMo6O23(OH)] [monoclinic, space group P21/c, a = 9.5587(1) A, b = 24.1364(2) A, c = 18.2788(2) A, beta = 90.1562(5) degrees , Z = 2], [(n-C4H9)4N]3[IMo6O22(OH)2].2DMF [monoclinic, space group P21/a, a = 17.6105(4) A, b = 15.5432(5) A, c = 29.3316(9) A, beta = 91.475(3) degrees , Z = 4], [(n-C4H9)4N]4[IMo6O23(OMe)].3H2O [orthorhombic, space group Pbca, a = 17.0679(4) A, b = 25.6998(6) A, c = 20.7428(4) A, Z = 4], [(n-C4H9)4N]3[IMo6O22(OMe)2] [monoclinic, space group P21/n, a = 10.4009(1) A, b = 14.6658(3) A, c = 23.5395(4) A, beta = 100.324(1) degrees , Z = 2]. In all of these compounds, the [IMo6O24]5- anion is protonated or methylated selectively at O atoms shared by two Mo atoms. The results have also revealed that the protonated Anderson-type molybdoperiodates readily react with methanol in a very selective manner, while the unprotonated [IMo6O24]5- anion does not react with methanol under similar conditions.

Icosaniobate: a new member of the isoniobate family.

Icosaniobate [Nb20O54]8- was synthesized by reacting [H4Nb6O19]4- with NO in tetrahydrofuran or MeNO2. A single-crystal X-ray diffraction study of its n-tetrabutylammonium salt [a = 17.7284(18) A, b = 33.542(3) A, c = 34.316(2) A, Z = 4, and space group P22(1)2(1)] revealed a dimeric structure where two decaniobate ions are condensed sharing two terminal O atoms. Unlike that in [(NbW5O18)2O]4-, the Nb-O-Nb bridges in icosaniobate are bent. The nonlinear bridging reduces the maximum possible symmetry of the dimeric anion to mm2, which it closely approximates.

Methoxide of an Anderson-type polyoxometalate and its conversion to a new type of species, [IMo9O32(OH)(OH2)3]4-.

A totally new type of polyoxometalate, [IMo(9)O(32)(OH)(OH(2))(3)](4)(-), has been synthesized by reacting [IMo(6)O(22)(OMe)(2)](3)(-) with water. The [IMo(9)O(32)(OH)(OH(2))(3)](4)(-) anion further transforms into [(IMo(7)O(26))(2)](6)(-), a molecular oxide that has a rutile core, in dry acetonitrile, while it stays intact for several hours in wet acetonitrile.

[(IMo(7)O(26))(2)](6)(-): A missing link between molecular and solid oxides.

A new molecular oxide, [(IMo(7)O(26))(2)](6)(-), that has a self-contained structure has been synthesized. Its structural relevance both to the rutile structure and several molecular oxides that had been classified as "strange ones with odd structures" has given some insights as to why those species assume such structures. The novel yet self-contained nature of the structure suggests the existence of a new class of molecular oxides of related structures.

(Et4N)4[V4O12].2H2O.

The title compound, tetrakis(tetraethylammonium) cyclo-tetra-micro-oxo-tetrakis[dioxovanadium(V)] dihydrate, (C(8)H(20)N)(4)[V(4)O(12)].2H(2)O, was obtained by reacting V(2)O(5) with (C(2)H(5))(4)NOH. It consists of a discrete centrosymmetric molecular anion, [V(4)O(12)](4-), where four tetrahedral VO(4) units share two vertices with each other to form a ring. A water molecule is attached on each side of the ring through hydrogen bonds.