Enhanced π‐Backdonation from Gold(I): Isolation of Original Carbonyl and Carbene Complexes

The specific electronic properties of bent o‐carborane diphosphine gold(I) fragments were exploited to obtain the first classical carbonyl complex of gold [(DPCb)AuCO]⁺ (ν(CO)=2143 cm^?1) and the diphenylcarbene complex [(DPCb)Au(CPh₂)]⁺, which is stabilized by the gold fragment rather than the carbene substituents. These two complexes were characterized by spectroscopic and crystallographic means. The [(DPCb)Au]⁺ fragment plays a major role in their stability, as substantiated by DFT calculations. The bending induced by the diphosphine ligand substantially enhances π‐backdonation and thereby allows the isolation of carbonyl and carbene complexes featuring significant π‐bond character.     

Photocatalytic Water Oxidation by a Pyrochlore Oxide upon Irradiation with Visible Light: Rhodium Substitution Into Yttrium Titanate

A stable visible‐light‐driven photocatalyst (λ≥450 nm) for water oxidation is reported. Rhodium substitution into the pyrochlore Y₂Ti₂O₇ is demonstrated by monitoring Vegard′s law evolution of the unit‐cell parameters with changing rhodium content, to a maximum content of 3 % dopant. Substitution renders the solid solutions visible‐light active. The overall rate of oxygen evolution is comparable to WO₃ but with superior light‐harvesting and surface‐area‐normalized turnover rates, making Y₂Ti_1.94Rh_0.06O₇ an excellent candidate for use in a Z‐scheme water‐splitting system.     

Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) combines the advantages of both ring-opening polymerization and radical polymerization thereby allowing the robust production of polyesters coupled with the mild polymerization conditions of a radical process. rROP was recently rejuvenated by the possibility to copolymerize CKAs with classic vinyl monomers leading to the insertion of cleavable functionality into a vinyl-based copolymer backbone and thus imparting (bio)degradability. Such materials are suitable for a large scope of applications, particularly within the biomedical field. The competition between the ring-opening and ring-retaining propagation routes is a major complication in the development of efficient CKA monomers, ultimately leading to the use of only four monomers that are known to completely ring-open under all experimental conditions. In this article we investigate the radical ring-opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict in silico the ring-opening ability of CKA monomers.     

Gold(III) π-Allyl Complexes

Gold(III) π-complexes have been authenticated recently with alkenes, alkynes, and arenes. The key importance of Pd^II π-allyl complexes in organometallic chemistry (Tsuji–Trost reaction) prompted us to explore gold(III) π-allyl complexes, which have remained elusive so far. The (P,C)Au^III(allyl) and (methallyl) complexes 3 and 3′ were readily prepared and isolated as thermally and air-stable solids. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi-symmetric η³-coordination of the allyl moiety. The π-allyl gold(III) complexes are activated towards nucleophilic additions, as substantiated with β-diketo enolates.     

Synthesis of a C(sp2)-bridged Phosphine-Borane by Ionic Coupling

The vinyl carbenoid H₂C=CBr(Li) has been used as key precursor to prepare a geminal C(sp²)-bridged phosphine-borane. Starting from bromoethene, two sequences of lithiation/electrophilic trapping, with ClPiPr₂ and FBMes₂ respectively, affords iPr₂P–C(=CH₂)–BMes₂ 3 [Mes = 2,4,6-(H₃C)₃C₆H₂]. This new phosphine-borane 3 was characterized by multi-nuclear NMR and mass spectroscopy. It adopts a monomeric open structure without P→B interaction. A few crystals of a secondary product 4 were analyzed by X-ray diffraction, revealing an unusual dimeric structure.     

Recent developments in the synthesis and functionalization of conducting poly(thiophenes)

The mechanism of the electropolymerization of thiophene derivatives has been investigated by varying the electrosynthesis conditions and the monomer structure. The results of these analyses led to the definition of optimized electrosynthesis conditions allowing the control of the electrical and electrochemical properties of poly(thiophenes). On the basis of these results, the properties of these polymers have been modified by means of a new one-step electrosynthesis of conducting composite materials and by the direct electropolymerization of tailor-made functionalized monomers. For this purpose, the steric conditions associated to the various possibilities of covalent derivatization have been analyzed, leading to the definition of a “functionalization space”, compatible with the preservation of high conductivity and electrochemical reversibility in the resulting polymers. This concept has been applied to the synthesis of highly conducting chiral poly(thiophenes) on which an effect of enantioselective molecular recognition has been demonstrated for the first time.     

Substituent effect in anionic polymerization of β-lactones initiated by alkali metal alkoxides

The influence of methyl substituent on the mechanism of the ring-opening polymerization of β-lactones initiated by alkali metal alkoxides is discussed. Attention has been paid to the effect of the substituent position in the monomer molecule on the ring-opening mechanism, the 3,3-dimethyl-2-oxetanone (pivalolactone), 4-methyl-2-oxetanone (β-butyrolactone) and 2-oxetanone (β-propiolactone) being chosen as model monomers. Moreover, it was found unexpectedly that in the case of pivalolactone polymerization, besides open-chain polymers, cyclic oligomers are produced.     

Energy filtered transmission electron microscopy for the physico-chemical characterization of aquatic submicron colloids

A combination of energy filtered transmission electron microscopic (EF-TEM) procedures is proposed for the non-perturbing physico-chemical characterization of submicron mineral and organic colloids in aquatic systems. Synthetic hematite microparticles and xanthan polysaccharides were used as well-characterized model colloids in order to determine the optimum EF-TEM analysis conditions. In this paper, it is demonstrated that (i) our model colloids are morphologically representative of naturally occurring mineral/organic associations, (ii) EF-TEM allows the detection of fine xanthan ultrastructures without artefacts of conventional staining methods and (iii) submicron hematite particles can be specifically visualized and spectrometrically measured by EF-TEM within a hematite/xanthan mixture. This EF-TEM procedure appears to be appropriate for the characterization of real aquatic samples.     

High temperature NMR approach of mixtures of rare earth and alkali fluorides: An insight into the local structure

In situ high temperature nuclear magnetic resonance in molten fluoride mixtures gives some structural picture of the complexes existing in the melt, i.e. of their nature and relative proportion. Thanks to the development of a laser heating system associated with a close crucible in boron nitride, we can describe experimentally the evolution of these complexes from the anions and the cations point of view. By ¹⁹F NMR, we have shown the existence of three kinds of fluorine atoms depending on the composition: free fluorine like in pure LiF (non-bonded), bridging fluorine in melts rich in LnF₃ in addition with terminal fluorine singly bonded to one rare earth. Data obtained by NMR spectroscopy are also combined with EXAFS measurements, again thanks to a specific development of the sample holder adapted with molten fluorides and high temperature. This study is a part of our systematic investigation of the different Alk-LnF₃ systems by NMR and EXAFS spectroscopy.     

Reducing methane formation in methanol to olefins reaction on metal impregnated SAPO-34 molecular sieve

SAPO-34 silicoaluminophosphate molecular sieve produces large amounts of methane at elevated temperatures in the methanol to olefins (MTO) process. This significantly reduces the lower olefins selectivity a key factor in determining the commercial viability of this catalyst. Impregnation of the SAPO-34 molecular sieve with metal ions such as K, Cs, Pt, Ag and Ce was found to reduce the amount of methane significantly at higher temperatures thereby increasing the lower olefins selectivity. This observed effect is less apparent at lower temperatures where the amount of methane formed is generally low. This revised version was published online in June 2006 with corrections to the Cover Date.