Versatile Organic Chemistry on Vanadium-Based Multi-Electron Reservoirs.

We report the synthesis, post-functionalization, and redox behavior of two organically functionalized aggregates, [V O (OMe) {(OCH ) C-CH N }] and [V O (OMe) {(OCH ) C-NH }]. All twelve μ -oxo groups on the edges of the Lindqvist-type {V O } core were replaced by alkoxo ligands. The absence of a negative charge and the closed organic shell make these neutral mixed-valence compounds very stable towards hydrolysis and well soluble in almost all common organic solvents.

Functional polyoxometalates from solvothermal reactions of VOSO with tripodal alkoxides - a study on the reactivity of different "tris" derivatives.

We report a study on the structure directing effects of functional groups and counterions. The aim was to find a facile and high yielding synthetic procedure to obtain polyoxometalate (POM) building blocks for post-functionalisation. Therefore, solvothermal reactions of VOSO with various tris(hydroxymethyl)methane derivatives in alkaline methanolic solutions were investigated.

[Fe19 ] "Super-Lindqvist" Aggregate and Large 3D Interpenetrating Coordination Polymer from Solvothermal Reactions of [Fe2 (OtBu)6 ] with Ethanol.

The syntheses, crystal structures, and physical properties of [HFe19 O14 (OEt)30 ] and {Fe11 (OEt)24 }∞ are reported. [HFe19 O14 (OEt)30 ] has an octahedral shape. Its core with a central Fe metal ion surrounded by six μ6 -oxo ligands is arranged in the rock salt structure.

Fluoridonitrosyl complexes of technetium(I) and technetium(II). Synthesis, characterization, reactions, and DFT calculations.

A mixture of [Tc(NO)F5](2-) and [Tc(NO)(NH3)4F](+) is formed during the reaction of pertechnetate with acetohydroxamic acid (Haha) in aqueous HF. The blue pentafluoridonitrosyltechnetate(II) has been isolated in crystalline form as potassium and rubidium salts, while the orange-red ammine complex crystallizes as bifluoride or PF6(-) salts. Reactions of [Tc(NO)F5](2-) salts with HCl give the corresponding [Tc(NO)Cl4/5](-/2-) complexes, while reflux in neat pyridine (py) results in the formation of the technetium(I) cation [Tc(NO)(py)4F](+), which can be crystallized as hexafluoridophosphate.

Hexafluoridotechnetate(IV) revisited.

Novel synthetic routes to hexafluoridotechnetate(IV) are reported, and for the first time the single-crystal X-ray structures of several M2[TcF6] salts (M = Na, K, Rb, Cs, NH4, and NMe4) were determined. The ammonium and the alkaline metal salts crystallize in the trigonal space group P3m, while the NMe4(+) salt belongs to the space group R3. [TcF6](2-) salts are widely stable in aqueous solution.

Exchange interactions and electron delocalization in the mixed-valence cluster V(4)(IV)V(2)(V)O(7)(OC(2)H(5))(12).

The mixed-valence cluster compound V4IVV2VO7(OC2H5)12 was studied by X-band electron paramagnetic resonance (EPR) in the temperature range of 4.2-293 K. According to X-ray diffraction study, the crystal structure of the compound was described by a R3m space group at 295 K (four d1 electrons are equally delocalized on all vanadium ions) and changed to a P21/n space group on cooling the crystals to 173 K (the electrons are preferably localized on the four equatorial vanadium ions).

Infrared, Raman, and DFT vibrational spectroscopic studies of C60F36 and C60F48.

IR and Raman spectra of two fluorofullerenes, C60F48 and C60F36, are thoroughly studied. Assignment of the experimental spectra is provided on the basis of density functional theory (DFT) computations. Perfect correspondence between experimental and computed spectra enabled us to confirm that the major isomer of C60F48 has D3 symmetry.

Synthesis, characterization, and theoretical study of stable isomers of C70(CF3)n (n = 2, 4, 6, 8, 10).

Reaction of C70 with ten equivalents of silver(I) trifluoroacetate at 320-340 degrees C followed by fractional sublimation at 420-540 degrees C and HPLC processing led to the isolation of a single abundant isomer of C70(CF3)n for n = 2, 4, 6, and 10, and two abundant isomers of C70(CF3)8. These six compounds were characterized by using matrix-assisted laser desorption ionization (MALDI) mass spectrometry, 2D-COSY and/or 1D 19F NMR spectroscopy, and quantum-chemical calculations at the density functional theory (DFT) level. Some were also characterized by Raman spectroscopy.

Solvothermal Synthesis of a 24-Nuclear, Cube-Shaped Squarato-oxovanadium(IV) Framework: [N(nBu) ] [V O (C O ) (OCH ) ].

Polydentate bridging ligands can be used to link small polyoxo-alkoxo-metalate units to form supramolecular clusters. In the title compound, twelve μ -bridging squarato groups connect eight trinuclear methoxo-oxo-vanadate units to form a tetradodecanuclear cubic framework, in whose cavity six n-butyl groups of the tetra-n-butylammonium cations are anchored.