CuLn complexes with a single μ-oximato bridge

Two original dinuclear (LnYb, 3 and LnEr, 4) and one trinuclear Cu^IILn^IIICu^II (LnGd, 5) complexes derived from a polydentate non symmetrical Schiff base ligand H₂L have been prepared. The ligand possesses two functions (phenol and oxime) able to coordinate the Ln ions, but structural studies (X-ray diffraction and powder X-ray diffraction) show that the Cu^II and Ln^III ions are only bridged by the oximato (NO) pair. The missing phenoxo bridge is replaced by a surprising pseudo-bridge involving one oxygen atom of the nitrato anion linked to the Cu and Ln ions according to a η²: η¹: μ mode. Although this latter contact has no role from the magnetic point of view, it introduces a large deformation of the unique bridging network. The CuYb complex 3 and the trinuclear CuGdCu complex 5 present antiferromagnetic interactions, with a J_CuGd interaction equal to ?1.25 cm^?1 in 5. The genuine single bridge can be considered as responsible for the antiferromagnetic character of the interaction.     

Sterically congested uranyl complexes with seven-coordination of the UO2 unit: the peculiar ligation mode of nitrate in [UO2(NO3)2(Rbtp)] complexes

Addition of 1 or 2 molar equiv of Rbtp [Rbtp = 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine; R = Me, Pr ( n )] to UO 2(OTf) 2 in anhydrous acetonitrile gave the neutral compounds [UO 2(OTf) 2(Rbtp)] [R = Me ( 1), ( n )Pr ( 2)] and the cationic complexes [UO 2(Rbtp) 2][OTf] 2 [R = Me ( 3), Pr ( n ) ( 4)], respectively. No equilibrium between the mono and bis(Rbtp) complexes or between [UO 2(Rbtp) 2][OTf] 2 and free Rbtp in acetonitrile was detected by NMR spectroscopy. The crystal structures of 1 and 3 resemble those of their terpyridine analogues, and 3 is another example of a uranyl complex with the uranium atom in the unusual rhombohedral environment. In the presence of 1 molar equiv of Rbtp in acetonitrile, UO 2(NO 3) 2 was in equilibrium with [UO 2(NO 3) 2(Rbtp)] and the formation of the bis adduct was not observed, even with an excess of Rbtp. The X-ray crystal structures of [UO 2(NO 3) 2(Rbtp)] [R = Me ( 5), Pr ( n ) ( 6)] reveal a particular coordination geometry with seven coordinating atoms around the UO 2 fragment. The large steric crowding in the equatorial girdle forces the bidentate nitrate ligands to be almost perpendicular to the mean equatorial plane, inducing bending of the UO 2 fragment. The dinuclear oxo compound [U(CyMe 4btbp) 2(mu-O)UO 2(NO 3) 3][OTf] ( 7), which was obtained fortuitously from a 1:2:1 mixture of U(OTf) 4, CyMe 4btbp, and UO 2(NO 3) 2 [CyMe 4btbp = 6,6'-bis-(3,3,6,6-tetramethyl-cyclohexane-1,2,4-triazin-3-yl)-2,2'-bipyridine] is a very rare example of a mixed valence complex involving covalently bound U (IV) and U (VI) ions; its crystal structure also exhibits a seven coordinate uranyl moiety, with one bidentate nitrate group almost parallel to the UO 2 fragment. The distinct structural features of [UO 2(kappa (2)-NO 3) 2(Mebtp)], with its high coordination number and a noticeable bending of the UO 2 fragment, and of [UO 2(kappa (2)-NO 3)(kappa (1)-NO 3)(terpy)], which displays a classical geometry, were analyzed by Density Functional Theory, considering the bonding energy components and the molecular orbitals involved in the interaction between the uranyl, nitrate, and Mebtp or terpy moieties. The unusual geometry of the Mebtp derivative with the seven coordinating atoms around the UO 2 fragment was found very stable. In both the Mebtp and terpy complexes, the origin of the interaction appears to be primarily steric (Pauli repulsion and electrostatic); this term represents 62-63% of the total bonding energy while the orbital term contributes to about 37-38%.     

The determination of organochlorine compounds and petroleum hydrocarbons in a seaweed sample: results of a world-wide intercomparison exercise

A seaweed sample (Fucus sp.) was prepared, homogenised and distributed to laboratories worldwide as the IAEA-140 intercomparison material for the analysis of organochlorine compounds and petroleum hydrocarbons. A total of 80 laboratories from 51 countries reported results for this sample. The data sets reported by laboratories were evaluated statistically and the mean concentration values could be computed with 95% confidence limits for a large number of analytes. The accuracy of the analytical performance of each laboratory has been introduced by using Z-scores. The spread of results reported generally indicates that the accurate determination of many persistent organic pollutants, such as hexachlorobenzene, lindane, Aroclors or fluoranthene, is still difficult for many laboratories. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-140 can now be used as a reference material for quality control in the determination of chlorinated compounds and petroleum hydrocarbons in environmental samples.     

Design of oxide nanoparticles by aqueous chemistry

The elaboration of nanoparticles designed for technological applications in various fields such as catalysis, optics, magnetism, electronics… needs the strict control of their characteristics, especially chemical composition, crystalline structure, size, and shape. These characteristics bring the physical properties (color, magnetism, band gap…) of the material, and also the surface to volume ratio of particles which is of high importance when they are used as a chemically active or reactive support, in catalysis for instance. The nanoparticles may have also to be surface functionalized by various species, and/or dispersed in aqueous or non aqueous media. We will show that the aqueous chemistry of metal cations is a very versatile and attractive way for the design of oxide nanomaterials, allowing the control of size, shape, and crystalline structure for polymorphic materials. Aqueous surface chemistry, including adsorption of various species, may be used to modify the morphology of nanoparticles. In some cases, redox processes can be involved to control the morphology of nanoparticles. Technologically important nanomaterials such as titania, alumina, and iron oxides are studied.     

A variety of spin-crossover behaviors depending on the counter anion: two-dimensional complexes constructed by NH...Cl- hydrogen bonds, [FeIIH3LMe]Cl.X (X = PF6 -, AsF6 -, SbF6 -, CF3SO3 -; H3L(Me) = Tris[2-{[(2-methylimidazol-4-yl)methylidene]amino}ethyl]amine)

A family of spin-crossover (SC) complexes, [Fe(II)H(3)L(Me)]Cl.X (X(-) = PF(6) (-), AsF(6) (-), SbF(6) (-), CF(3)SO(3) (-)), 1-4, has been synthesized, in which H(3)L(Me) denotes the hexadentate N(6) tripod-like ligand tris[2-{[(2-methylimidazol-4-yl)methylidene]amino}ethyl]amine, containing three imidazole groups, with a view to establishing the effect of the counter anion on the SC behavior. These complexes have been found to crystallize in the same monoclinic crystal system with similar cell dimensions. The general crystal structure consists of a two-dimensional (2D) extended network constructed by NH...Cl- hydrogen bonds between Cl- and the imidazole NH groups of three neighboring [Fe(II)H(3)L(Me)]2+ ions, while the anion X exists as an isolated counter anion and occupies the space between the 2D sheets. Magnetic susceptibilities and M?ssbauer spectra have revealed a variety of SC behaviors depending on the counter anion, including a one-step HS<==>(HS + LS)/2 (1, X = PF(6) (-)), a two-step HS<==>(HS + LS)/2<==>LS with a slow thermal relaxation (2, X = AsF(6) (-)), a gradual one-step HS<==>LS (3, X = SbF(6) (-)), and a steep one-step HS<==>LS with hysteresis (4, X = CF(3)SO(3) (-)). The complexes assume the space group P2(1)/n in the HS state, P2(1) in the HS + LS state, and P2(1)/n in the LS state. The Fe-N bond lengths and the N-Fe-N bond angles are indicative of the HS, HS + LS, and LS states. The molecular volumes, V, of the counter anions have been evaluated by quantum-chemical calculations as follows: 53.4 A(3) (BF(4) (-)), 54.4 A(3) (ClO(4) (-)), 73.0 A(3) (PF(6) (-)), 78.5 A(3) (AsF(6) (-)), 88.7 A(3) (SbF(6) (-)), and 86.9 A(3) (CF(3)SO(3) (-)). The size and shape of the counter anion affects the flexible 2D network structure constructed by the hydrogen bonds, leading to modifications of the SC behavior. These estimated relative sizes of the counter anions correlate well with the observed SC behaviors.     

Monomeric iron(II) hydroxo and iron(III) dihydroxo complexes stabilized by intermolecular hydrogen bonding

Using the multidentate ligand bis(N-methylimidazol-2-yl)-3-methylthiopropanol (L), the mononuclear iron(II) hydroxo and iron(III) dihydroxo complexes [Fe(II)(L)2(OH)](BF4) (1) and [Fe(III)(L)2(OH)2](BF4) (2) have been synthesized and characterized by X-ray diffraction and spectroscopic methods. The X-ray data suggest that the remarkable stability of the Fe-OH bond(s) in both compounds results from intermolecular hydrogen-bonding interactions between the hydroxo ligand(s) and the tertiary hydroxyl of the L ligands, which prevent further intermolecular reactions.     

AB initio study of the regular polyhedral molecules N4, P4, As4, N8, P8 and As8

Ab initio pseudopotential SCF calculations were performed on tetrahedral X₄ molecules using double-zeta basis sets with and without d functions. The inclusion of d orbitals shortens the bond lengths, stabilizes the X₄ structures and intensifies the electron density inside the tetrahedron. The cubic X₈ molecules, calculated without d AOs, are not predicted to be more stable than 2X₄. Repulsions between parallel bonds in X₈ may compensate the lack of ring strain.     

High-spin to low-spin relaxation kinetics in the [Fe(TRIM)2]Cl2 complex

A quasi-quantitative photo-induced low-spin (LS)-->high-spin (HS) conversion of FeII ions has been observed in the [Fe(TRIM)2]Cl2 complex by irradiating the sample with blue light (488 nm) at 10 K. The time dependence of the HS-->LS relaxation has been studied between 10 K and 44 K by means of magnetic susceptibility measurements. These relaxation curves could be satisfactorily fitted by mono-exponential decays including tunnelling effect except for temperatures below 30 K. The introduction of a distribution of vibrational frequencies into this model improved significantly the fits in the low-temperature range and gave a good agreement with the experimental data in the whole temperature range suggesting a multi-rate relaxation process in this complex.     

Synthese et reactivite d''organometalliques perfluores. VII [1] reactivite comparee de derives perfluoroalkyles satures et insatures de l''etain et du mercure vis-a-vis d''electrophiles.

The reactivity of some derivatives of perfluorooctenyl-tin, perfluorooctenyl-mercury and perfluorooctyl-mercury towards protic acids, especially hydrogen chloride, is studied.

The easy cleavage of the tin - sp² carbon bond is painted out, and used to study possibilities of transferring the perfluorooctenyl radical on mercury, upon reaction with mercuric salts.

The mercury-perfluoroalkyl radical bond is shown to be, on the contrary, very resistant to an electrophilic attack.

These results are compared to those concerning the hydrocarbon analogs, and an interpretation, relied to the electronic density on the carbon atom bound to the metallic atom, is given.     

Photocyclisation d'hydroxyalkyl glycosides en orthoesters glycosidiques

A free-radical cyclization process makes glycosidic orthoester structures readily available in a one-pot procedure.