Synthesis of imidazolium-based pentacoordinated organofluorosilicate and germanate salts.

The syntheses of a new triphenyldifluorogermanate and various pentacoordinated organofluorosilicates are presented. The fluorogermane and fluorosilane compounds were obtained from the corresponding chlorosilanes and chlorogermane by halogen substitution with KF. Subsequent reaction with the imidazolium-based fluoride reagent [IPrH][F] (1,3-bis(2,6-diisopropylphenyl)imidazolium fluoride) led to the formation of [IPrH][PhSiF] (1), [IPrH][PhSiF] (3), [IPrH][EtSiF] (4), [IPrH][PhSiF] (5), [IPrH][EtSiF] (6) and [IPrH][PhGeF] (7).

Trideset let delovanja Šole eksperimentalne kemije na Institutu "Jožef Stefan": trideset let motiviranja mladih generacij in utrjevanja poti naravoslovnega izobraževanja.

Pred 30. leti, natančneje spomladi leta 1992, je bila, v okviru Odseka za anorgansko kemijo in tehnologijo Instituta "Jožef Stefan", ustanovljena Šola eksperimentalne kemije. Zaradi razvoja znanosti in interdisciplinarnih pristopov, je njen glavni namen približevanje kemije mladim generacijam in prikazovanje njene širše uporabe v vsakdanjem življenju.

Coordination of a Neutral Ligand to a Metal Center of Oxohalido Anions: Fact or Fiction?

Can a neutral ligand bond to a metal center of a square pyramidal oxohalido anion at the available sixth octahedral position? Crystal structures of some compounds indeed suggest that ligands, such as THF, pyridine, HO, NH, and CHCN, can interact with the central metal atom, because they are oriented with their heteroatom toward the metal center with distances being within the bonding range. However, this assumption that is based on chemical intuition is wrong. In-depth analysis of interactions between ligands and oxohalido anions (e.

Reactivity of VOF with N-Heterocyclic Carbene and Imidazolium Fluoride: Analysis of Ligand-VOF Bonding with Evidence of a Minute π Back-Donation of Fluoride.

Reaction of vanadium(V) oxide trifluoride (VOF) and the new "naked" fluoride reagent [(L)H][F] (L = 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2 H-imidazol-2-ylidene) leads to the isolation of [(L)H][VOF] (1) where the long sought discrete [VOF] anion was finally obtained. The neutral [(L)VOF] (2) complex was synthesized by a similar reaction between VOF and bulky N-heterocyclic carbene (NHC) ligand L. In this context, we analyzed, by means of DFT calculations, intermolecular interactions between [(L)VOF] (2) complexes in the crystal structure and realized that these interactions have a significant effect on the V-F bond length.

Discrete GeF Anion Structurally Characterized with a Readily Synthesized Imidazolium Based Naked Fluoride Reagent.

The recently prepared novel naked fluoride reagent 1,3-bis(2,6-diisopropylphenyl)imidazolium fluoride ([(L)H][F]), treated with an excess of MF (M = Si, Ge), results in isolation of [(L)H][MF] products with the elusive trigonal bipyramidal MF anions. Specific steric characteristics of the [(L)H] cation readily support isolation of monomeric and discrete trigonal bipyramidal fluorido anions of silicon and germanium. Based on combination of experimental results and DFT calculations, we demonstrate that the role of bulky cation is not solely due to steric hindering but also due to electrostatic effects, which are important in the design of such uncommon species.

Oxidation of Ruthenium and Iridium Metal by XeF2 and Crystal Structure Determination of [Xe2F3][RuF6]·XeF2 and [Xe2F3][MF6] (M = Ru, Ir).

Salts containing [Xe2F3]+ cations and [MF6]- anions (M = Ru, Ir) were synthesized by the oxidation of metal with excess of XeF2 in anhydrous hydrogen fluoride (aHF) as a solvent. Single crystals of [Xe2F3][RuF6]·XeF2, [Xe2F3][RuF6] and [Xe2F3][IrF6] were grown by slow evaporation of the solvent. [Xe2F3][RuF6]·XeF2 crystallizes in a triclinic P-1 space group (a = 8.

Synthesis and crystal structures of lanthanoid(III) hexafluoroarsenates with AsF3 ligands.

Lanthanoid(III) hexafluoroarsenates with AsF3 as a ligand were prepared with the reactions of solutions of Ln(AsF6)3 in anhydrous hydrogen fluoride and AsF3. Solid products with composition Ln(AsF3)3(AsF6)3 (Ln = La, Nd, Sm, Eu, Gd, Tb, Er, Tm) were isolated at 233 K. The attempt to prepare corresponding Yb and Lu compounds failed.

Solid-state NMR spectroscopic study of coordination compounds of XeF(2) with metal cations and the crystal structure of [Ba(XeF(2))(5)][AsF(6)](2).

The coordination compounds [Mg(XeF(2))(2)][AsF(6)](2), [Mg(XeF(2))(4)][AsF(6)](2), [Ca(XeF(2))(2.5)][AsF(6)](2), [Ba(XeF(2))(3)][AsF(6)](2), and [Ba(XeF(2))(5)][AsF(60](2) were characterized by solid-state (19)F and (129)Xe magic-angle spinning NMR spectroscopy. The (19)F and (129)Xe NMR data of [Mg(XeF(2))(2)][AsF(6)](2), [Mg(XeF(2)(4)][AsF(6)](2), and [Ca(XeF(2))(2.

Metal(II) hexafluorophosphates(V) (M = Sr, Pb) containing XeF(2)-coordinated metal ions [M(XeF(2))(3)](PF(6))(2), [Pb(3)(XeF(2))(11)](PF(6))(6), and [Sr(3)(XeF(2))(10)](PF(6))(6).

From the system MF(2)/PF(5)/XeF(2)/anhydrous hydrogen fluoride (aHF), four compounds [Sr(XeF(2))(3)](PF(6))(2), [Pb(XeF(2))(3)](PF(6))(2), [Sr(3)(XeF(2))(10)](PF(6))(6), and [Pb(3)(XeF(2))(11)](PF(6))(6) were isolated and characterized by Raman spectroscopy and X-ray single-crystal diffraction. The [M(XeF(2))(3)](PF(6))(2) (M = Sr, Pb) compounds are isostructural with the previously reported [Sr(XeF(2))(3)](AsF(6))(2). The structure of [Sr(3)(XeF(2))(10)](PF(6))(6) (space group C2/c; a = 11.

Coordination of XeF2 to calcium and cadmium hexafluorophosphates(V).

[M(XeF2)5](PF6)2 (M = Ca, Cd) complexes were prepared by the reaction of MF2 and XeF2 under pressure of gaseous PF5 in anhydrous HF as solvent. The coordination sphere of the Ca atom consists of nine fluorine atoms: three from two PF6(-) units (one bidentate and one monodentate) and one from each of six XeF2 molecules. The coordination sphere of the Cd atom consists of eight fluorine atoms: one from each of two PF6(-) units and one from each of six XeF2 molecules.

[Mg(XeF(2))(n)()](AsF(6))(2) (n = 4, 2): first compounds of magnesium with XeF(2).

The reaction between Mg(AsF(6))(2) and XeF(2) in anhydrous HF (aHF) at room temperature yields two compounds with XeF(2) bonded directly to the Mg(2+) cation: [Mg(XeF(2))(4)](AsF(6))(2); [Mg(XeF(2))(2)](AsF(6))(2). The 1:4 compound is obtained with excess XeF(2) while the 1:2 compound is prepared from stoichiometric amounts of Mg(AsF(6))(2) and XeF(2). [Mg(XeF(2))(4)](AsF(6))(2) crystallizes in an orthorhombic crystal system, space group P2(1)2(1)2(1), with a = 8.