Eu Moessbauer spectroscopy. The structure of EuCd2As2 is determined by single crystal XRD (space group P3m1, Z = 1; CaAl2Si2 type structure). The two-dimensional [Cd2X2] (X: P, As, Sb) networks of the title compounds consist of edge-sharing CdX 4 tetrahedra. The networks are separated and charge-balanced by europium and ytterbium atoms. Redetermination of the magnetic properties revealed divalent europium and ytterbium. YbCd2Sb2 is diamagnetic. The europium compounds exhibit only one magnetic phase transition.

Hydroboration of dimesitylnorbornenylphosphane with Piers' borane [HB(C6F5)2] gave the frustrated Lewis pair (FLP) 4 in good yield. It has the -PMes2 Lewis base attached at the 2-endo position and the -B(C6F5)2 group 3-exo oriented at the norbornane framework. The vicinal FLP 4 was shown by X-ray diffraction and by spectroscopy to be a rare example of an intramolecular noninteracting pair of a Lewis acid and Lewis base functionality. The FLP 4 rapidly splits dihydrogen heterolytically at ambient temperature to yield the phosphonium/hydrido borate zwitterion 5. It adds to the carbonyl group of benzaldehyde and to carbon dioxide to yield the adducts 6 and 7, respectively. Compounds 5-7 were characterized by X-ray diffraction. Compound 4 adds to the S═O function of sulfur dioxide to give a pair of diastereomeric heterocyclic six-membered ring products due to the newly formed sulfur chirality center, annulated with the norbornane skeleton, which were investigated by (31)P/(11)B single and double resonance solid state NMR experiments. Compound 8 was also characterized by X-ray diffraction. The FLP 4 undergoes a clean N,N-addition to nitric oxide (NO) to give a norbornane annulated five-membered heterocyclic persistent FLP-NO aminoxyl radical 12 (characterized, e.g., by X-ray diffraction and EPR spectroscopy). Additionally, the FLP radical was characterized by (1)H solid state NMR spectroscopy. The radical 12 undergoes a H-atom abstraction reaction with 1,4-cyclohexadiene to yield the respective diamagnetic FLP-NOH product 13, which was also characterized by X-ray diffraction and solid state NMR spectroscopy.

International audienceNew YbMo2Al4-type cadmium compounds CaAu4Cd2, SrAu4Cd2, and EuAu4Cd2 were synthesized from the elements in sealed tantalum tubes. The structures of CaAu4Cd2 (I4/mmm, a = 710.7(1), c = 550.2(3) pm, wR2 = 0.026, 168 F 2 values, 10 variables) and EuAu4.80Cd1.20 (a = 716.6(1), c = 545.9(1) pm, wR2 = 0.024, 167 F 2 values, 11 variables) were refined from X-ray single-crystal diffractometry data. The gold and cadmium atoms show different substructures: Au4 squares (279 pm Au-Au in CaAu4Cd2) and cadmium chains (275 pm Cd-Cd in CaAu4Cd2). EuAu4Cd2 forms a solid solution EuAu4+x Cd2−x up to x ≈ 1, where almost every other cadmium atom within the chains is substituted by gold. Chemical bonding analyses on CaAu4Cd2 shows almost complete charge transfer from calcium to the [Au4Cd2] network. Bader charge analysis classifies CaAu4Cd2 as an auride. EuAu4Cd2 shows Curie-Weiss behavior above 25 K with an experimental magnetic moment of 7.86 μB/Eu atom, near to the free ion value of 7.94 μB for Eu2+ and orders ferromagnetically at T C = 16.3(5) K. 151Eu Mössbauer spectra show a single signal at an isomer shift of about −10 mm/s, compatible with divalent europium. At 5 K, and therefore clearly below T C, magnetic hyperfine splitting is observed

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Hybrid materials, in which stable organic radical cations are intercalated into layered inorganic host materials, can be successfully synthesized via an ion exchange reaction in a layered fluoromica clay, to yield recyclable heterogeneous catalysts for oxidation of various alcohols. We have conducted systematic synthetic and structural studies on the intercalation of the radical cations 4-(diethylmethylammonium)-2,2,6,6-tetramethylpiperidin-1-oxyl (DEMTEP), 1-[2-(4-amino-2,2,6,6-tetramethyl-1-piperidinyloxyl)-2-oxoethyl]-1'-methyl-4,4'-bipyridinium (VIOTEP), and 2-(3-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide (m-MPYNN) into a synthetic fluoromica clay named Somasif® ME 100, Na(2x)Mg(3.0-x)Si4O10(F(y)OH(1-y))2 (x = 0.33, y = 0.98). The guest-host interactions in these intercalation compounds have been characterized by X-ray powder diffraction and solid-state NMR of the constituent nuclei ((23)Na, (19)F, and (29)Si) of the Somasif structure. The intercalation process can be conveniently monitored using (23)Na MAS-NMR. Guest-guest interactions have been probed by magnetic susceptibility measurements as well as EPR and (1)H MAS NMR experiments. The (1)H MAS-NMR line widths and chemical shifts probe modifications in the electron spin density distributions and/or intermolecular interactions between the electron spins of the guest species. Despite these indications of weakly interacting spins, magnetic susceptibility measurements are consistent with the near-absence of cooperative magnetism. The VIOTEP and DEMTEP inclusion compounds demonstrate catalytic activity for the oxidation of benzyl alcohol, using NaOCl as a co-oxidant. Although the radical ion species is partially leached out under these conditions (ionic exchange with Na(+) in solution) the catalytic activity remains for up to 40 subsequent cycles. Fully leached materials can be regenerated by catalyst re-loading and this process can be conveniently monitored by X-band EPR spectroscopy.

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The reaction of either V(2)F(6)·4H(2)O or a mixture of 60 wt % VF(2)·4H(2)O and 40 wt % VF(3)·3H(2)O with a water-saturated gaseous mixture of 15-20 vol % hydrogen in argon leads to the formation of a new polymorph of V(3)O(5) crystallizing in the orthorhombic anosovite-type structure. Quantum-chemical calculations show that the anosovite-type structure is about 15 kJ/mol less stable than the corresponding monoclinic Magnéli phase. In addition, there are no imaginary modes in the phonon density of states, supporting the classification of the anosovite-type phase as a metastable V(3)O(5) polymorph. Susceptibility measurements down to 3 K reveal no hint for magnetic ordering.