Adducts of Rh2[MTPA]4 with some phosphine chalcogenides: nature of binding and ligand exchange

Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group.     

3,7-Dioxaazelaamides as Ionophores for Lithium Ion Selective Liquid Membrane Electrodes

Lipophilic neutral carriers were synthesized which show Li⁺/Na⁺ selectivities of up to ca. 80 in highly lipophilic liquid membranes. The sensor membranes exhibit improved response times and increased lifetimes as compared to systems described earlier. They allow reliable measurements of Li⁺ in blood serum within the clinical concentration range. A 1:1 Li⁺/ionophore complex of one representative (N,N,N′,N′-tetracyclohexyl-5,5-dimethyl-3,7-dioxaazelaamide) has been prepared, and its structure was elucidated by X-ray analysis.     

Insights into the structure of cyclohexane from femtosecond degenerate four-wave mixing spectroscopy and ab initio calculations

In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixing rotationally resolved spectroscopy to obtain very accurate structural information on the symmetric top cyclohexane. Apart from highlighting the versatility of this method in determining accurate structures of large and complex molecules without dipole moment, the present study also details the comparison of the experimentally determined rotational constant B(0) with that obtained from high-level ab initio calculations. The theoretical calculations, which were carried out at both the second-order M?ller-Plesset (MP2) and coupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, also take into account vibrational averaging effects. A detailed investigation of the vibrational averaging effects reveals that the corrections emerge from only the six highly symmetric A(1g) modes, a justification of which is provided by an analysis of these modes.     

Methylmethacrylate complexes of sterically hindered aluminum aryloxides: activation of methacrylic esters

The interaction of AlR₂(BHT)(OEt₂) and AlMe(BHT)₂ with methylmethacrylate (MMA) leads to the formation of the Lewis acid-base complexes AlR₂(BHT)(MMA) [R = Me (1), Et (2)] and AlMe-(BHT)₂(MMA) (3), respectively. The molecular structure of 1 has been determined by X-ray crystallography. The decrease in the C=O and C=C stretching frequencies in the IR spectrum, and downfield shift in the ¹³C NMR spectrum of the - and γ-carbons of the MMA, when compared to free MMA, is presented with respect to the activator ability of sterically crowded aryloxide compounds of aluminum to aluminum-porphyrin catalyzed (Inoue) polymerization of MMA.     

The CeO(2)(+) Cation: Gas-Phase Reactivity and Electronic Structure

"Bare" CeO(2)(+) ions can be prepared in the gas phase by consecutive oxidation of Ce(+) with O(2) and NO(2). The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO(2)(+) with linear and branched alkanes C-H bond activation is observed almost exclusively. In contrast, both oxygen-atom transfer and C-H bond activation processes occur when thermalized CeO(2)(+) cations react with simple alkenes and aromatic compounds. C-C bond activation is not observed at all. Insight into the structural and electronic properties of neutral CeO(2) and cationic CeO(2)(+) is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a (2)Sigma(u)(+) ground state for CeO(2)(+) which is best described as a linear cerium dioxide with a resonating pi bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO(n)()(+) (n = 0-2) species toward hydrocarbons.     

ESR study of free radicals in some new hydrazones of terpenoids class

The effect of gamma-irradiation on some new hydrazones of terpenoids using electron spin resonance (ESR) is reported. Gamma-irradiation of three derivates of hydrazone and of compounds resulting from the condensation of these derivates with terpenoids produces stable free radicals at room temperature. The analysis of the ESR parameters (g-factors and hyperfine coupling) and the simulation performed lead us to conclude that free radicals are of form R–N–NH₂ (arising from hydrazine derivates) and R–N–N=R (arising from condensation compounds). The thermal stability of formed radicals is discussed and the activation energy involved in the process of recombination of free radicals is calculated.