Merging organometallic chemistry with polyoxometalate chemistry

A series of polyoxomolybdate-incorporated organometallic complexes has been obtained by reaction of [MBr(CO)5] or solvated M(CO)3+ ions (M = Mn or Br) with (nBu4N)2[Mo2O7] in methanol, sometimes in the presence of triols of the type RC(CH2OH)3 (R = Me or CH2OH). Their molecular structures are related to those of previously described polyoxoalkoxomolybdates through the formal replacement of fac-MoO2(OR)+ units by topologically equivalent fac-M(CO)3+ units. Representative pairs of structurally related clusters include [Mo2O6(OMe)4-Re(CO)32]2- and [Mo4O10(OMe)6]2-, [Mo2O4MeC(CH2O)32Mn(CO)3]- and [Mo3O6(OMe)MeC(CH2O)32]-, [Mo2O4HOCH2C(CH2O)32Mn(CO)32] and [Mo4O8(OEt)2MeC(CH2O)32], [Mo6O16(OMe)2MeC(CH2O)32-Mn(CO)32]2- and [Mo8O20(OMe)4-MeC(CH2O)32]2-. Although the frameworks of the majority of derivatives are based on tetranuclear units which display the common rhomb-like structure, the alternative cubane-type arrangement is observed in [Mo2O5(OMe)5M(CO)32]-.     

Modeling a neutron-rich nuclei source

The deuteron break-up process in a suitable converter gives rise to intense neutron beams. A source of neutron-rich nuclei based on the neutron-induced fission can be realised using these beams. A theoretical optimization of such a facility as a function of the incident deuteron energy is reported. The model used to determine the fission products takes into account the excitation energy of the target nucleus and the evaporation of prompt neutrons. Results are presented in connection with a converter-target specific geometry. Received: 1 December 2000 / Accepted: 12 May 2001     

The EC networking on elemental speciation revisited

In Europe, the EC-funded Thematic Network Speciation 21 was instrumental in disseminating the existing knowledge about chemical speciation of trace elements. It created a forum in which analytical chemists working in method development were mixed with potential users from industry and representatives of legislative bodies. This endeavour is continuing in the currently established European Virtual Institute for Speciation Analysis (EVISA). Although there already exists substantial know-how in Europe for the speciation of a number of substances, such as organo-arsenic, organo-tin and organo-mercury compounds, to name just these three groups, there is an urgent need to enforce the analytical potential in speciation analysis on a much wider scope of compounds capable of providing data of a suitable quality. The ensuing need for quality assurance of the analytical procedures requires the analysis of representative reference materials, certified for the relevant species. Last but not least, where applicable, the European-wide legislation should be adapted to focus on toxic species of the elements, rather than the total element.Presented at BERM-9—Ninth International Symposium on Biological and Environmental Reference Materials, June 15–19, 2003, Berlin, Germany. Disclaimer The opinions expressed in the present article are entirely those of the authors. They do not represent the opinion of the European Community.     

Test of the Wiedemann-Franz law in an optimally doped cuprate

We present a study of heat and charge transport in Bi(2+x)Sr(2-x)CuO(6+delta) focused on the size of the low-temperature linear term of the thermal conductivity at optimal-doping level. In the superconducting state, the magnitude of this term implies a d-wave gap with an amplitude close to what has been reported. In the normal state, recovered by the application of a magnetic field, measurement of this term and residual resistivity yields a Lorenz number L=kappa(N)rho(0)/T=1.3+/-0.2L(0). The departure from the value expected by the Wiedemann-Franz law is thus slightly larger than our estimated experimental resolution.     

Functionalization of polyoxometalates: from Lindqvist to Keggin derivatives. 1. synthesis, solution studies, and spectroscopic and ESI mass spectrometry characterization of the rhenium phenylimido tungstophosphate [PW11O39(ReNC6H5)]4-

Reaction of [Bu(4)N](4)[H(3)PW(11)O(39)] with [Re(NPh)Cl(3)(PPh(3))(2)], in acetonitrile and in the presence of NEt(3), provided the first Keggin-type organoimido derivative [Bu(4)N](4)[PW(11)O(39)(ReNPh)] (Ph = C(6)H(5)) (1). The functionalization was clearly demonstrated by various techniques including (1)H and (14)N NMR, electrochemistry, and ESI mass spectrometry. Conditions for the formation of 1 are also discussed.     

Pickering Emulsion Stabilized by Catalytic Polyoxometalate Nanoparticles: A New Effective Medium for Oxidation Reactions

Decyl‐, dodecyl‐, and tetradecyltrimethylammonium cations were combined with the catalytic polyoxometalate [PW₁₂O₄₀]^3? anion to give spherical and monodisperse nanoparticles that are able to stabilize emulsions in the presence of water and an aromatic solvent. This triphasic liquid/solid/liquid system, based on a catalytic surfactant, is particularly efficient as a reaction medium for epoxidation reactions that involve hydrogen peroxide. The reactions proceed at competitive rates with straightforward separation of the phases by centrifugation. Such catalytic “Pickering” emulsions combine the advantages of heterogeneous catalysis and biphasic catalysis without the drawbacks (e.g., catalyst leaching or separation time).     

Functionalized heteropolyanions: high-valent metal nitrido fragments incorporated into a Keggin polyoxometalate structure

Three examples of nitrido-functionalized polyoxometalate species are reported, namely (n-Bu4N)4[PW11O39(OsN)] (1), (n-Bu4N)4[PW11O39(ReN)] (2), and (n-Bu4N)3[PW11O39(ReN)] (3), which feature the incorporation of [OsVI identical to N]3+, [ReVI identical to N]3+ and [ReVII identical to N]4+ fragments, respectively, into the framework of a Keggin-type heteropolyanion.     

Coordination chemistry of the soluble metal oxide analogue [Mo5O13(OCH3)4(NO)]3- with manganese carbonyl species

The reactions of neutral or cationic manganese carbonyl species towards the oxo-nitrosyl complex [Na(MeOH)[Mo(5)O(13)(OCH(3))(4)(NO)]](2-) have been investigated in various conditions. This system provides an unique opportunity for probing the basic reactions involved in the preparation of solid oxide-supported heterogeneous catalysts, that is, mobility of transition-metal species at the surface and dissolution-precipitation of the support. Under nitrogen and in the dark, the reaction of in situ generated fac-[Mn(CO)(3)](+) species with (nBu(4)N)(2)[Na(MeOH)-[Mo(5)O(13)(OMe)(4)(NO)]] in MeOH yields (nBu(4)N)(2)[Mn(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]] at room temperature, while (nBu(4)N)(3)[Na[Mo(5)O(13)(OMe)(4)(NO)](2)[Mn(CO)(3)](2)] is obtained under reflux. The former transforms into the latter under reflux in methanol in the presence of sodium bromide; this involves the migration of the fac-[Mn(CO)(3)](+) moiety from a basal kappa(2)O coordination site to a lateral kappa(3)O site. Oxidation and decarbonylation of manganese carbonyl species as well as degradation of the oxonitrosyl starting material and reaggregation of oxo(methoxo)molybdenum fragments occur in non-deareated MeOH, and both (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(16)(OMe)(2)](2)[Mn(CO)(3)](2)] and (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(13)(OMe)(4)(NO)](2)] as well as (nBu(4)N)(2)[MnBr[Mo(5)O(13)(OMe)(4)(NO)]] have been obtained in this way. The rhenium analogue (nBu(4)N)(2)[Re(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]] has also been synthesized. The crystal structures of (nBu(4)N)(2)[Re(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]], (nBu(4)N)(3)[Na[Mo(5)O(13)(OMe)(4)(NO)](2)[Mn(CO)(3)](2)], (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(16)(OMe)(2)](2)[Mn(CO)(3)](2)], (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(13)(OMe)(4)(NO)](2)] and (nBu(4)N)(2)[MnBr[Mo(5)O(13)(OMe)(4)(NO)]] have been determined.     

In-Situ Synthesis and Characterization of Nanocomposites in the Si-Ti-N and Si-Ti-C Systems

The pyrolysis (1000 °C) of a liquid poly(vinylmethyl-co-methyl)silazane modified by tetrakis(dimethylamido)titanium in flowing ammonia, nitrogen and argon followed by the annealing (1000–1800 °C) of as-pyrolyzed ceramic powders have been investigated in detail. We first provide a comprehensive mechanistic study of the polymer-to-ceramic conversion based on TG experiments coupled with in-situ mass spectrometry and ex-situ solid-state NMR and FTIR spectroscopies of both the chemically modified polymer and the pyrolysis intermediates. The pyrolysis leads to X-ray amorphous materials with chemical bonding and ceramic yields controlled by the nature of the atmosphere. Then, the structural evolution of the amorphous network of ammonia-, nitrogen- and argon-treated ceramics has been studied above 1000 °C under nitrogen and argon by X-ray diffraction and electron microscopy. HRTEM images coupled with XRD confirm the formation of nanocomposites after annealing at 1400 °C. Their unique nanostructural feature appears to be the result of both the molecular origin of the materials and the nature of the atmosphere used during pyrolysis. Samples are composed of an amorphous Si-based ceramic matrix in which TiN_xC_y nanocrystals (x + y = 1) are homogeneously formed “in situ” in the matrix during the process and evolve toward fully crystallized compounds as TiN/Si₃N₄, TiN_xC_y (x + y = 1)/SiC and TiC/SiC nanocomposites after annealing to 1800 °C as a function of the atmosphere.