Exploring Cu/Al cluster growth and reactivity: from embryonic building blocks to intermetalloid,open-shell superatoms

Cluster growth reactions in the system [Cu₅](Mes)₅ + [Al₄](Cp*)₄ (Mes = mesitylene, Cp* = pentamethylcyclopentadiene) were explored and monitored by in situ LIFDI-MS and ¹H-NMR. Feedback into experimental design allowed for an informed choice and precise adjustment of reaction conditions and led to isolation of the intermetallic cluster [Cu₄Al₄](Cp*)₅(Mes) (1). Cluster 1 reacts with excess 3-hexyne to yield the triangular cluster [Cu₂Al](Cp*)₃ (2). The two embryonic [Cu₄Al₄](Cp*)₅(Mes) and [Cu₂Al](Cp*)₃ clusters 1 and 2, respectively, were shown to be intermediates in the formation of an inseparable composite of the closely related clusters [Cu₇Al₆](Cp*)₆ (3), [HCu₇Al₆](Cp*)₆ (3H) and [Cu₈Al₆](Cp*)₆ (4), which just differ by one Cu core atom. The radical nature of the open-shell superatomic [Cu₇Al₆](Cp*)₆ cluster 3 is reflected in its reactivity towards addition of one Cu core atom leading to the closed shell superatom [Cu₈Al₆](Cp*)₆ (4), and as well by its ability to undergo σ(C–H) and σ(Si–H) activation reactions of C₆H₅CH₃ (toluene) and (TMS)₃SiH (TMS = tris(trimethylsilyl)).

Cu/Al cluster growth reactions leading to open- and closed-shell superatoms are investigated. Therein, LIFDI-MS is presented as a powerful technique for the in situ detection of cluster identities and reactivity patterns.     

Towards relative invariants of real symplectic four-manifolds

Let (X, ω, c_X) be a real symplectic four-manifold with real part . Let be a smooth curve such that We construct invariants under deformation of the quadruple (X, ω, c_X, L) by counting the number of real rational J-holomorphic curves which realize a given homology class d, pass through an appropriate number of points and are tangent to L. As an application, we prove a relation between the count of real rational J-holomorphic curves done in [W2] and the count of reducible real rational curves done in [W3]. Finally, we show how these techniques also allow us to extract an integer valued invariant from a classical problem of real enumerative geometry, namely about counting the number of real plane conics tangent to five given generic real conics. Received: March 2005; Revision: September 2005; Accepted: September 2005     

Access to a new family of medium ring aromatic lactones

We report a new method for preparation of hydroxyacids as precursors of benzolactones using a simple and an efficient electrochemical step. This gives in only four steps six- to eleven-membered lactones with high isolated yields from conveniently substituted aryl bromides. The lactonisation was performed according to the Yamamoto's process.     

Bonding Analysis of Square-Antiprismatic and Fused Square-Antiprismatic Copper(I)-Selenium Clusters

The electronic structure of the Cu_2(4n+2)Se_4n+2(PH₃)₈ (n = 1–4) D _4h series of model clusters has been analyzed by means of density functional theory calculations. The fused square antiprismatic structure of the metal framework is found to be always preferred over the fused cuboctahedral one because it reinforces the Cu-P bonds. Thus, the presence of the terminal phosphine ligands tends to strengthen the Cu...Cu (d¹⁰...d¹⁰) bonding by mixing bonding combinations of the vacant Cu 4s and 4p orbitals into the occupied 3d combinations. The calculations indicate that the compounds corresponding to n = 3 and 4 should be easily two-electron-reduced, leading to stable dianionic species.     

Hybrid copolymer latexes cross-linked with methacryloxy propyl trimethoxy silane. Film formation and mechanical properties

We describe in this work the copolymerization reaction of 3-trimethoxysilyl propyl methacrylate (MPS) with styrene (Styr.) and n-butyl acrylate (BuA) monomers through emulsion polymerization. The so-produced hybrid copolymer (P(BuA-co-MPS)) and terpolymer (P(Styr-co-BuA-co-MPS)) latexes were cast into films that displayed a good optical transparency. The copolymers microstructure in the films was characterized by FTIR, ¹³C and ²⁹Si solid state NMR spectroscopies, and was found to be highly dependent on parameters such as the monomer feed composition, the suspension pH and the silane addition profile. The films obtained from the hybrid latexes showed improved dynamic mechanical properties indicating that a reinforcing organo-mineral network had formed in the composite materials. The dynamic modulus of the hybrids increased with increasing silane contents while, concurrently, the tan δ peak shifted to higher temperatures, broadened and decreased in intensity. To cite this article: S. Vitry et al., C. R. Chimie 6 (2003).     

In situ characterisation of a microorganism surface by Raman microspectroscopy: the shell of Ascaris eggs

Intestinal nematodes are very common human parasites and a single species, Ascaris lumbricoïdes, is estimated to infect a quarter of the world’s population. A sticky external layer covers their eggs. This work shows that Raman vibrational confocal spectroscopy is able to give information on the biochemical composition of the shell of Ascaris eggs. The biochemical localised characterisation of Ascaris eggs was performed directly on the eggs in their aqueous environment. The studied parasites came from two origins: dissections of adult females and extractions from biosolid sludges. The presence of mucopolysaccharides, proteins and chitin in the shell was demonstrated. The presence of ascaroside compounds was shown particularly via the narrow and intense bands from the organised long CH₂ chains. To the best of our knowledge, this is the first time that the latter have been observed in Raman vibrational spectra of microorganisms. Hydration of the shell was different depending on the intensity of the colour of the sludge eggs. Knowledge of the biochemical structural properties of egg surfaces would be useful to understand the egg adhesion phenomena on vegetables contaminated by reused wastewater.     

Two new hybrid organic/inorganic copper(II)-oxovanadate(V) diphosphonates: [Cu2(phen)2(O3PCH2PO3)(V2O5)(H2O)] x H2O and [Cu2(phen)2(O3P(CH2)3PO3)(V2O5)] x C3H8. Synthesis, structure, and magnetic properties

Two new hybrid organic/inorganic copper oxovanadium diphosphonates [Cu2(phen)2(O3PCH2PO3)(V2O5)(H2O)] x H2O (1) and [(Cu2(phen)2(O3P(CH2)3PO3)(V2O5)] x C3H8 (2) have been obtained by hydrothermal synthesis. The compounds are monoclinic, and they crystallize in the space group P2(1)/n with cell parameters of a = 11.788(2) A, b = 17.887(3) A, c = 14.158(2) A, and beta = 93.99(0) degrees and in the space group C2/c with cell parameters of a = 11.025(1) A, b = 18.664(2) A, c = 15.054(2) A, and beta = 90.06(0) degrees, respectively. Both compounds present two-dimensional frameworks built up from infinite chains of corner-sharing vanadium tetrahedra and diphosphonate groups connected by copper tetramers for (1) and copper dimers for (2). The remarkable feature of (2) is the encapsulation of propane molecules, stabilized by strong hydrogen bonding between the layers. The magnetic properties of the compounds have been investigated showing antiferromagnetic coupling with Tmax = 64 K for (1) and Curie-like paramagnetic behavior for (2).     

Novel tert-butyl-tris(3-hydrocarbylpyrazol-1-yl)borate ligands: synthesis, spectroscopic studies, and coordination chemistry

The lithium (1) and thallium (2) salts of five new tert-butyl-tris(3-hydrocarbylpyrazol-1-yl)borate ligands [t-BuTp(R)]- (R = H, a; Me, b; i-Pr, c; t-Bu, d; Ph, e) have been synthesized and characterized. Because of steric congestion at B, the reaction between t-BuBH3Li x 0.5 Et2O and excess 2,5-dimethylpyrazole Hpz(Me2) afforded the bis-pz(Me2) derivative, Tl[t-BuBH(3,5-Me2pz)2] (3) after metathesis with TlNO3. The compounds were characterized by elemental analysis and NMR spectroscopy. The Li salts 1a and 1c exhibit fluxional behavior on the NMR time scale in solution at room temperature. The solid-state 7Li and 11B NMR spectra of 1c suggest that this salt exists as a mixture of axial and equatorial isomers. The partial hydrolysis of 1d afforded the dimeric Li complex {Li[t-BuB(pz(t-Bu))2(mu-OH)]}2 (4). The crystal structure of 4 shows two Li cations encapsulated by the heteroscorpionate [t-BuB(OH)(3-t-Bupz)2]- ligands. A salt elimination reaction between FeCl2(THF)1.5 and 2 equiv of Li[t-BuTp(R)] (R = H, Me) followed by an in situ one-electron oxidation produced good yields of the homoleptic, paramagnetic low-spin iron(III) complexes [Fe(t-BuTp)2]PF6 (5) and [Fe(t-BuTp(Me))2]PF6 (6) that were characterized by elemental analyses, magnetic susceptibility measurements in solution and the solid phase, 1H NMR, high-resolution mass spectrometry, M?ssbauer spectroscopy, and single-crystal X-ray diffraction. The crystals are composed of discrete molecular units with the central Fe(III) ion in an almost perfectly octahedral coordination to six nitrogen atoms. Compound 5 has the shortest Fe-N bond lengths ever reported for [Fe(RTp(R)')2]+-type compounds.