Replacement of Volatile Acetic Acid by Solid SiO@COOH Silica (Nano)Beads for (Ep)Oxidation Using Mn and Fe Complexes Containing BPMEN Ligand.

Mn and Fe BPMEN complexes showed excellent reactivity in catalytic oxidation with an excess of co-reagent (CHCOOH). In the straight line of a cleaner catalytic system, volatile acetic acid was replaced by (nano)particles with two different sizes to which pending carboxylic functions were added (). The beads were obtained by the functionalization of SiO with pending nitrile functions () followed by CN hydrolysis.

Triphenylphosphine-Functionalized Core-Cross-Linked Micelles and Nanogels with a Polycationic Outer Shell: Synthesis and Application in Rhodium-Catalyzed Biphasic Hydrogenations.

Unimolecular amphiphilic nanoreactors with a poly(4-vinyl-N-methylpyridinium iodide) (P4VPMe I ) polycationic outer shell and two different architectures (core-cross-linked micelles, CCM, and nanogels, NG), with narrow size distributions around 130-150 nm in diameter, were synthesized by RAFT polymerization from an R -4VPMe I -b-S -SC(S)SPr macroRAFT agent by either chain extension with a long (300 monomer units) hydrophobic polystyrene-based block followed by cross-linking with diethylene glycol dimethacrylate (DEGDMA) for the CCM particles, or by simultaneous chain extension and cross-linking for the NG particles. A core-anchored triphenylphosphine (TPP) ligand functionality was introduced by using 4-diphenylphosphinostyrene (DPPS) as a comonomer (5-20 % mol mol ) in the chain extension (for CCM) or chain extension/cross-linking (for NG) step. The products were directly obtained as stable colloidal dispersions in water (latexes).

Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation.

A latex of amphiphilic star polymer particles, functionalized in the hydrophobic core with nixantphos and containing P(MAA-co-PEOMA) linear chains in the hydrophilic shell (nixantphos-functionalized core-crosslinked micelles, or nixantphos@CCM), has been prepared in a one-pot three-step convergent synthesis using reversible addition-fragmentation chain transfer (RAFT) polymerization in water. The synthesis involves polymerization-induced self-assembly (PISA) in the second step and chain crosslinking with di(ethylene glycol) dimethacrylate (DEGDMA) in the final step. The core consists of a functionalized polystyrene, obtained by incorporation of a new nixantphos-functionalized styrene monomer (nixantphos-styrene), which is limited to 1 mol%.

Fluoroalkyl Pentacarbonylmanganese(I) Complexes as Initiators for the Radical (co)Polymerization of Fluoromonomers.

The use of [Mn(R)(CO)] (R = CF, CHF, CHCF COCFCH) to initiate the radical polymerization of vinylidene fluoride (FC=CH, VDF) and the radical alternating copolymerization of vinyl acetate (CH=CHOOCCH, VAc) with -butyl 2-(trifluoromethyl)acrylate (MAF-TBE) by generating primary R radicals is presented. Three different initiating methods with [Mn(CF)(CO)] (thermal at ca. 100 °C, visible light and UV irradiations) are described and compared.

Organic Solvent-Free Olefins and Alcohols (ep)oxidation Using Recoverable Catalysts Based on [PMO] (M = Mo or W) Ionically Grafted on Amino Functionalized Silica Nanobeads.

Catalyzed organic solvent-free (ep)oxidation were achieved using HPMO (M = Mo or W) complexes ionically grafted on APTES-functionalized nano-silica beads obtained from straightforward method (APTES = aminopropyltriethoxysilane). Those catalysts have been extensively analyzed through morphological studies (Dynamic Light Scattering (DLS), TEM) and several spectroscopic qualitative (IR, multinuclear solid-state NMR) and quantitative (H and P solution NMR) methods. Interesting catalytic results were obtained for the epoxidation of cyclooctene, cyclohexene, limonene and oxidation of cyclohexanol with a lower [POM]/olefin ratio.

Crystal structure of penta-carbon-yl(2,2-di-fluoro-propane-thio-ato-κ)manganese(I).

The title compound, [Mn{SC(O)CFCH}(CO)], has been isolated as a by-product during the reaction of K[Mn(CO)] with CHCFCOCl. It is built up from a di-fluoro-methyl-propane-thio-ate bonded to an Mn(CO) moiety through the S atom. The Mn atom has an almost perfect octa-hedral coordination sphere.

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives.

Thermal decarbonylation of the acyl compounds [Mn(CO) (COR )] (R =CF , CHF , CH CF , CF CH ) yielded the corresponding alkyl derivatives [Mn(CO) (R )], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn( CO) (eq- CO)(R )] and [Mn( CO) (ax- CO)(R )] isotopomers and a ranking of the R donor power in the order CF View Article and Find Full Text PDF

Bis(formylphenolato)cobalt(II)-Mediated Alternating Radical Copolymerization of tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate.

The organometallic-mediated radical polymerization (OMRP) of vinyl acetate (VAc) and its OMR copolymerization (OMRcoP) with -butyl 2-trifluoromethylacrylate (MAF-TBE) mediated by Co(SAL)₂ (SAL = 2-formylphenolato or deprotonated salicylaldehyde) produced relatively well-defined PVAc and poly(VAc--MAF-TBE) copolymers at moderate temperature (<40 °C) in bulk. The resulting alternating copolymer was characterized by ¹H-, C- and F-nuclear magnetic resonance (NMR) spectroscopies, and by size exclusion chromatography. The linear first-order kinetic plot, the linear evolutions of the molar mass with total monomer conversion, and the relatively low dispersity (~1.

Catalyzed Chain Transfer in Vinyl Acetate Polymerization Mediated by 9-Oxyphenalenone Cobalt(II) Complexes.

The vinyl acetate (VAc) radical polymerization initiated by V-70 at 30 °C in the presence of [Co(OPN)] (OPN = deprotonated 9-oxyphenalenone), , leads to PVAc of lower molecular weight (MW) than expected for organometallic-mediated radical polymerization (OMRP), whether reversible termination or degenerate transfer conditions are used. This represents the first clear evidence of catalyzed chain transfer (CCT) in VAc polymerization. The bis-pyridine adduct [Co(OPN)(py)], , shows a marginally lower polymerization rate and an increased CCT activity relative to , whereas the activity decreases with marginal effect on the polymerization rate upon addition of excess py.

Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.

Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene.

Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer Latexes.

A well-defined amphiphilic core-shell polymer functionalized with bis(-methoxy-phenylphosphino)phenylphosphine (BMOPPP) in the nanogel (NG) core has been obtained by a convergent RAFT polymerization in emulsion. This BMOPPP@NG and the previously-reported TPP@NG (TPP = triphenylphosphine) and core cross-linked micelles (L@CCM; L = TPP, BMOPPP) having a slightly different architecture were loaded with [Rh(acac)(CO)₂] or [RhCl(COD)]₂ to yield [Rh(acac)(CO)(L@Pol)] or [RhCl(COD)(L@Pol)] (Pol = CCM, NG). The interparticle metal migration from [Rh(acac)(CO)(TPP@NG)] to TPP@NG is fast at natural pH and much slower at high pH, the rate not depending significantly on the polymer architecture (CCM NG).

Core-shell nanoreactors for efficient aqueous biphasic catalysis.

Water-borne phosphine-functionalized core-cross-linked micelles (CCM) consisting of a hydrophobic core and a hydrophilic shell were obtained as stable latexes by reversible addition-fragmentation chain transfer (RAFT) in water in a one-pot, three-step process. Initial homogeneous aqueous-phase copolymerization of methacrylic acid (MAA) and poly(ethylene oxide) methyl ether methacrylate (PEOMA) is followed by copolymerization of styrene (S) and 4-diphenylphosphinostyrene (DPPS), yielding P(MAA-co-PEOMA)-b-P(S-co-DPPS) amphiphilic block copolymer micelles (M) by polymerization-induced self-assembly (PISA), and final micellar cross-linking with a mixture of S and diethylene glycol dimethacrylate. The CCM were characterized by dynamic light scattering and NMR spectroscopy to evaluate size, dispersity, stability, and the swelling ability of various organic substrates.

Positionable vertical microfluidic cell based on electromigration in a theta pipet.

A microscale vertical fluidic cell system has been implemented, based on a simple theta pipet pulled to a sharp point (ca. 10-20 μm diameter for the studies herein) and positioned with a high degree of control on a surface. The dual channel arrangement allows an electric field to be generated between an electrode in each compartment of the pipet that can be used to control the electromigration of charged species between the two compartments, across a thin liquid meniscus in contact with the substrate of interest.

Preparation of phosphine-functionalized polystyrene stars by metal catalyzed controlled radical copolymerization and their application to hydroformylation catalysis.

Well defined star copolymers have been prepared by copper-catalyzed atom transfer radical copolymerization of styrene and styryldiphenylphosphine starting from a modified Boltorn™ H30 multifunctional initiator. These polymers and an analogue obtained by debromination of the arm ends with nBu3SnH have been used in combination with [Rh(acac)(CO)2] for the homogeneous phase hydroformylation of 1-octene.

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) as a probe of macromolecule adsorption kinetics at functionalized interfaces.

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) has been employed to study the interfacial adsorption kinetics of coumarin-tagged macromolecules onto a range of functionalized planar surfaces. Such studies are valuable in designing polymers for complex systems where the degree of interaction between the polymer and surface needs to be tailored. Three tagged synthetic polymers with different functionalities are examined: poly(acrylic acid) (PAA), poly(3-sulfopropyl methacrylate, potassium salt) (PSPMA), and a mannose-modified glycopolymer.

High internal phase emulsion gels (HIPE-gels) from polymer dispersions reinforced with quadruple hydrogen bond functionality.

A convenient route to organogels templated by high internal phase emulsions has been developed. Key is the use of a waterborne polymer latex loaded with a multiple hydrogen bond (MHB) functionality that becomes disentangled and transfers across the oil-water interface forming a gel network in the oil phase via hydrogen bond interactions.

Vesicles in ionic liquids.

The formation of vesicles from 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) in several room-temperature ionic liquids, namely, 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF(4)), 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF(6)), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf(2)), and N-benzylpyridinium bis(trifluoromethylsulfonyl)imide (BnPyNTf(2)), as well as in a water/BmimBF(4) mixture, was investigated. In pure ionic liquids, observations by staining transmission electron microscopy demonstrated clearly the formation of spherical structures with diameters of 200-400 nm. The morphological characteristics of these vesicles in ionic liquids, in particular, the membrane thicknesses, were first investigated by small-angle neutron scattering measurements.

Ionic liquid/oil microemulsions as chemical nanoreactors.

The phase diagram and microstructure of the ternary system ionic, liquid benzylpyridinium bis(trifluoromethanesulfonyl)imide)/nonionic surfactant (octylphenol ethoxylate)/toluene, were studied by using conductivity measurements, dynamic light scattering, pulse field gradient spin-echo NMR, and small-angle neutron scattering. Three microregions were identified by conductivity measurements according to the percolation theory. The sizes of IL-in-oil microemulsions with various IL fractions were then determined by NMR and DLS and were found to be in accordance with the radii of gyration (approximately 2 or 3 nm) determined by SANS.