Thierry Roisnel

WinPLOTR: A Windows Tool for Powder Diffraction Pattern Analysis

WinPLOTR is a graphic program for the analysis of powder diffraction patterns. It has been developed for a Windows 9x/2k/NT environment. It takes advantage of this graphical environment to offer a powerful and user-friendly powder diffraction tool. The program is able to display and analyse many different kinds of diffraction patterns as well as calculated and observed profiles coming from the Windows/DOS version of the program FullProf. It can also be used as a Graphic User Interface (GUI) for programs defined by the user.

Polymerization of enantiopure monomers using syndiospecific catalysts: a new approach to sequence control in polymer synthesis.

The ring-opening polymerization of a mixture of enantiomerically pure but different monomers using an yttrium complex as initiator proceeds readily at room temperature to give the corresponding highly alternating polyester.

Discrete, solvent-free alkaline-earth metal cations: metal···fluorine interactions and ROP catalytic activity.

Efficient protocols for the syntheses of well-defined, solvent-free cations of the large alkaline-earth (Ae) metals (Ca, Sr, Ba) and their smaller Zn and Mg analogues have been designed. The reaction of 2,4-di-tert-butyl-6-(morpholinomethyl)phenol ({LO(1)}H), 2-{[bis(2-methoxyethyl)amino]methyl}-4,6-di-tert-butylphenol ({LO(2)}H), 2-[(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)methyl]-4,6-di-tert-butylphenol ({LO(3)}H), and 2-[(1,4,7,10-tetraoxa-13-azacyclo-pentadecan-13-yl)methyl]-1,1,1,3,3,3-hexafluoropropan-2-ol ({RO(3)}H) with [H(OEt(2))(2)](+)[H(2)N{B(C(6)F(5))(3)}(2)](-) readily afforded the doubly acidic pro-ligands [{LO(1)}HH](+)[X](-) (1), [{LO(2)}HH](+)[X](-) (2), [{LO(3)}HH](+)[X](-) (3), and [{RO(3)}HH](+)[X](-) (4) ([X](-) = [H(2)N{B(C(6)F(5))(3)}(2)](-)). The addition of 2 to Ca[N(SiMe(3))(2)](2)(THF)(2) and Sr[N(SiMe(3))(2)](2)(THF)(2) yielded [{LO(2)}Ca(THF)(0.5)](+)[X](-) (5) and [{LO(2)}Sr(THF)](+)[X](-) (6), respectively. Alternatively, 5 could also be prepared upon treatment of {LO(2)}CaN(SiMe(3))(2) (7) with [H(OEt(2))(2)](+)[X](-). Complexes [{LO(3)}M](+)[X](-) (M = Zn, 8; Mg, 9; Ca, 10; Sr, 11; Ba, 12) and [{RO(3)}M](+)[X](-) (M = Zn, 13; Mg, 14; Ca, 15; Sr, 16; Ba, 17) were synthesized in high yields (70-90%) by reaction of 3 or 4 with the neutral precursors M[N(SiMe(3))(2)](2)(THF)(x) (M = Zn, Mg, x = 0; M = Ca, Sr, Ba, x = 2). All compounds were fully characterized by spectroscopic methods, and the solid-sate structures of compounds 1, 3, 7, 8, 13, 14, {15}(4)·3CD(2)Cl(2), {16}(4)·3CD(2)Cl(2), and {{17}(4)·EtOH}·3CD(2)Cl(2) were determined by X-ray diffraction crystallography. Whereas the complexes are monomeric in the case of Zn and Mg, they form bimetallic cations in the case of Ca, Sr and Ba; there is no contact between the metal and the weakly coordinating anion. In all metal complexes, the multidentate ligand is κ(6)-coordinated to the metal. Strong intramolecular M···F secondary interactions between the metal and F atoms from the ancillary ligands are observed in the structures of {15}(4)·3CD(2)Cl(2), {16}(4)·3CD(2)Cl(2), and {{17}(4)·EtOH}·3CD(2)Cl(2). VT (19)F{(1)H} NMR provided no direct evidence that these interactions are maintained in solution; nevertheless, significant Ae···F energies of stabilization of 25-26 (Ca, Ba) and 40 kcal·mol(-1) (Sr) were calculated by NBO analysis on DFT-optimized structures. The identity and integrity of the cationic complexes are preserved in solution in the presence of an excess of alcohol (BnOH, (i)PrOH) or L-lactide (L-LA). Efficient binary catalytic systems for the immortal ring-opening polymerization of L-LA (up to 3,000 equiv) are produced upon addition of an excess (5-50 equiv) of external protic nucleophilic agents (BnOH, (i)PrOH) to 8-12 or 13-17. PLLAs with M(n) up to 35,000 g·mol(-1) were produced in a very controlled fashion (M(w)/M(n) ≈ 1.10-1.20) and without epimerization. In each series of catalysts, the following order of catalytic activity was established: Mg ≪ Zn < Ca < Sr ≈ Ba; also, Ae complexes supported by the aryloxide ligand are more active than their parents supported by the fluorinated alkoxide ancillary, possibly owing to the presence of Ae···F interactions in the latter case. The rate law -d[L-LA]/dt = k(p)·[L-LA](1.0)·[16](1.0)·[BnOH](1.0) was established by NMR kinetic investigations, with the corresponding activation parameters ΔH(++) = 14.8(5) kcal·mol(-1) and ΔS(++) = -7.6(2.0) cal·K(-1)·mol(-1). DFT calculations indicated that the observed order of catalytic activity matches an increase of the L-LA coordination energy onto the cationic metal centers with parallel decrease of the positive metal charge.

An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity

In oxides, the substitution of non-oxide anions (F(-),S(2-),N(3-) and so on) for oxide introduces many properties, but the least commonly encountered substitution is where the hydride anion (H(-)) replaces oxygen to form an oxyhydride. Only a handful of oxyhydrides have been reported, mainly with electropositive main group elements or as layered cobalt oxides with unusually low oxidation states. Here, we present an oxyhydride of the perhaps most well-known perovskite, BaTiO(3), as an O(2-)/H(-) solid solution with hydride concentrations up to 20% of the anion sites. BaTiO(3-x)H(x) is electronically conducting, and stable in air and water at ambient conditions. Furthermore, the hydride species is exchangeable with hydrogen gas at 400 °C. Such an exchange implies diffusion of hydride, and interesting diffusion mechanisms specific to hydrogen may be at play. Moreover, such a labile anion in an oxide framework should be useful in further expanding the mixed-anion chemistry of the solid state.

Surface modification of zinc oxide nanoparticles by aminopropyltriethoxysilane

Commercial zinc oxide nanoparticles (20–30 nm) were coated by aminopropyltriethoxysilane (APTES) under varying environments. Three different processes, acidic, basic and toluene were used. The effects of coating conditions (acidic, basic and toluene) on the grafting, structural and optical properties of these nanoparticles were studied. In the three cases, it was possible to control the coating and according to X-ray diffraction, BET, TEM and SEM results, it is clear that the APTES coating plays a role of growth inhibitor even at 800 °C...

Clustomesogens: Liquid Crystal Materials Containing Transition-Metal Clusters**

their integration in macro-scopic devices by a bottom-up approach remains a challenge.This task requires systems with self-organization abilities onthe one hand and fluidity on the other hand, to correctautomatically the positioning errors that can occur during theassembly process. Metal-containing liquid crystals (metal-lomesogens) are the typical examples in which the uniquepropertiesofanisotropic fluidsarecombined withthe specificproperties of metals (e.g. geometry of coordination, optic,electronic, magnetic).

When Bigger Is Better: Intermolecular Hydrofunctionalizations of Activated Alkenes Catalyzed by Heteroleptic Alkaline Earth Complexes

New alkaline-earth amido complexes catalyze the regioselective intermolecular hydroamination (see scheme; Ae=alkaline earth) and hydrophosphination of styrene and isoprene with unprecedented activities. The catalytic performances increased linearly with the size of the metal.

Selective Reduction of Esters to Aldehydes under the Catalysis of Well-Defined NHC–Iron Complexes†

A simple methodol. for the chemoselective redn. of esters to aldehydes with a N-heterocyclic-carbene-iron complex, such as [(IMes)-Fe(CO)4], as the catalyst (1 mol%) in the presence of a secondary silane (diethylsilane or diphenylsilane) as the reducing agent. has been developed. This reaction occurs at room temp. under UV irradn. with both arom. and aliph. esters. Notably, this catalytic system also permitted the efficient and selective redn. of lactones to lactols. Exptl. evidence indicated that the hydrosilylation occurs by oxidative addn. of the hydrosilane to an unsatd. NHC-Fe species to yield a silyl iron hydride complex. [on SciFinder(R)]

Iridium‐Catalyzed Oxidant‐Free Dehydrogenative CH Bond Functionalization: Selective Preparation of N‐Arylpiperidines through Tandem Hydrogen Transfers

In addition to creating efficient and selective methodologies, the rise of green chemistry has led organic chemists and chemical industry to take into account the impact of these processes on the environment. Among the different ecofriendly approaches, homogeneous metal-catalyzed hydrogen autotransfers aimed at developing benign and atom-efficient protocols for the construction of carbon–heteroatom or carbon–carbon bonds have attracted considerable interest. In these reactions, the transient formation of unsaturated carbonyl or imine intermediates, arising from the dehydrogenation of alcohols or amines acting as alkylating reagents, has been successfully used for the preparation of a-alkylated carbonyl derivatives and amines accompanied by the formation of either water or valuable ammonia as the only side product. Owing to the potential of these transformations, recent developments have focused on the preparation of welldefined ruthenium and iridium complexes to allow more selective and milder reaction conditions, water soluble or reusable catalysts, and continuous flow approaches. In addition, the appealing amination from ammonia to afford alkylated amines has been reported by several groups. However, to date no tandem methodologies based on hydrogen autotransfer involving three different partners have been reported. Recently, we achieved the unprecedented oxidant-free dehydrogenation of cyclic N-benzyl and N-alkylamines using a ruthenium(II)–arene catalyst (A ; Scheme 1) featuring a phosphinesulfonate chelate. This reactivity involves hydrogen autotransfers and was successfully applied to the

Heteroleptic silylamido phenolate complexes of calcium and the larger alkaline earth metals: β-agostic Ae⋅⋅⋅Si-H stabilization and activity in the ring-opening polymerization of L-lactide.

The factors governing the stability and the reactivity towards cyclic esters of heteroleptic complexes of the large alkaline earth metals (Ae) have been probed. The synthesis and stability of a family of heteroleptic silylamido and alkoxide complexes of calcium [{LO(i)}Ca-Nu(thf)(n)] supported by mono-anionic amino ether phenolate ligands (i = 1, {LO(1)}(-) = 4-(tert-butyl)-2,6-bis(morpholinomethyl)phenolate, Nu(-) = N(SiMe(2)H)(2)(-), n = 0, 4; i = 2, {LO(2)}(-) = 2,4-di-tert-butyl-6-{[2-(methoxymethyl)pyrrolidin-1-yl]methyl}phenolate, Nu(-) = N(SiMe(2)H)(2)(-), n = 0, 5; i = 4, {LO(4)}(-) = 2-{[bis(2-methoxyethyl)amino]methyl}-4,6-di-tert-butylphenolate, Nu(-) = N(SiMe(2)H)(2)(-), n = 1, 6; Nu(-) = HC≡CCH(2)O(-), n = 0, 7) and those of the related [{LO(3)}Ae-N(SiMe(2)H)(2)] ({LO(3)}(-) = 2-[(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)methyl]-4,6-di-tert-butylphenolate Ae = Ca, 1; Sr, 2; Ba, 3) have been investigated. The molecular structures of 1, 2, [(4)(2)], 6, and [(7)(2)] have been determined by X-ray diffraction. These highlight Ae⋅⋅⋅H-Si internal β-agostic interactions, which play a key role in the stabilization of [{LO(i)}Ae-N(SiMe(2)H)(2)] complexes against ligand redistribution reactions, in contrast to regular [{LO(i)}Ae-N(SiMe(3))(2)]. Pulse-gradient spin-echo (PGSE) NMR measurements showed that 1, 4, 6, and 7 are monomeric in solution. Complexes 1-7 mediate the ring-opening polymerization (ROP) of L-lactide highly efficiently, converting up to 5000 equivalents of monomer at 25 °C in a controlled fashion. In the immortal ROP performed with up to 100 equivalents of exogenous 9-anthracenylmethanol or benzyl or propargyl alcohols as a transfer agent, the activity of the catalyst increased with the size of the metal (1<2<3). For Ca-based complexes, the enhanced electron-donating ability of the ancillary ligand favored catalyst activity (1>6>4≈5). The nature of the alcohol had little effect over the activity of the binary catalyst system 1/ROH; in all cases, both the control and end-group fidelity were excellent. In the living ROP of L-LA, the HC≡CCH(2)O(-) initiating group (as in 7) proved superior to N(SiMe(2)H)(2)(-) or N(SiMe(3))(2)(-) (as in 6 or [{LO(4)}Ca-N(SiMe(3))(2)] (B), respectively).