Replacement of Toxic Hydrazines in Satellite Propulsion with Greener Dinitramide-Based Energetic Ionic Liquid Candidates.

Satellite propulsion uses liquid mono or bi-propellants composed of a hydrazine in combination with a strong oxidant. However, hydrazines are highly toxic. As a result, many research efforts for more environmentally compatible propellants have been made over the past decade. In this study we evidence green formulations that retain high propulsive performances. They are based on the dinitramide anion. From an initial library of 37 ammonium dinitramides 3 best candidates were selected after evaluation of their potential syntheses, calculated theoretical performances, experimental synthesis optimizations and decomposition temperatures. These three salts were then formulated to obtain acceptable sensitivities and melting points, which eventually led to only one formulation being retained: a 40 : 60 mixture of dimethylammonium dinitramide and ammonium dinitramide phlegmatized by 10 % of glycerol.

Catalyst-Free Transfer Hydrogenation from Amine-Borane Small Oligomers.

Amine-borane dimers and oligomers with varied steric and electronic profiles were prepared via capping agent-controlled AA/BB polycondensations. They were used for transfer hydrogenations to aldehydes, ketones, imines as well as electron-poor alkene/alkyne moieties. The amine-borane Lewis-paired oligomers and the congested bis(amine-borane)s provided the highest yields. This was likely helped by facilitated dissociation (oligomers) or H-bond assistance. In the case of the oligomers, the second equivalent of H2 present was also engaged in the reaction. Solid-state NMR characterization provides evidence that the boron-containing materials obtained after transfer dehydrogenation are highly similar to those obtained from thermal dehydrogenation. The oligomers bridge the gap between simple amine-borane molecular reductants and the poly-amine-boranes and provide a full picture of the reactivity changes at the different scales.

Visible-Light Initiated Dispersion Photopolymerization of Styrene.

Polystyrene (PS) particles were synthesized in ethanol/water mixture by dispersion polymerization using visible light irradiation, with either a N-heterocyclic carbene borane-based photoinitiating system (PIS) or a disulfide. With the full PIS and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as stabilizer, the size distributions were broad and the amount of PEGMA had a strong impact on the experiment reproducibility. The addition of a base solved the problem, leading to faster polymerizations, narrower size distributions and larger particles. With the disulfide as sole PIS, bigger and narrowly distributed PS particles were again formed. Quantitative conversion was achieved in each system, with particle size ranging between 100 and 350 nm. The use of poly(N-vinylpyrrolidone) as stabilizer led to significantly larger particles, up to 1.2 µm, with narrow size distributions. The production of such large latex particles by photoinitiated polymerizations is unprecedented.

NHC induced radical formation via homolytic cleavage of B-B bonds and its role in organic reactions.

New borylation methodologies have been reported recently, wherein diboron(4) compounds apparently participate in free radical couplings via the homolytic cleavage of the B-B bond. We report herein that bis-NHC adducts of the type (NHC)2·B2(OR)4, which are thermally unstable and undergo intramolecular ring expansion reactions (RER), are sources of boryl radicals of the type NHC-BR2˙, exemplified by Me2ImMe·Bneop˙ 1a (Me2ImMe = 1,3,4,5-tetramethyl-imidazolin-2-ylidene, neop = neopentylglycolato), which are formed by homolytic B-B bond cleavage. Attempts to apply the boryl moiety 1a in a metal-free borylation reaction by suppressing the RER failed. However, based on these findings, a protocol was developed using Me2ImMe·B2pin23 for the transition metal- and additive-free boryl transfer to substituted aryl iodides and bromides giving aryl boronate esters in good yields. Analysis of the side products and further studies concerning the reaction mechanism revealed that radicals are likely involved. An aryl radical was trapped by TEMPO, an EPR resonance, which was suggestive of a boron-based radical, was detected in situ, and running the reaction in styrene led to the formation of polystyrene. The isolation of a boronium cation side product, [(Me2ImMe)2·Bpin]+I-7, demonstrated the fate of the second boryl moiety of B2pin2. Interestingly, Me2ImMe NHC reacts with aryl iodides and bromides generating radicals. A mechanism for the boryl radical transfer from Me2ImMe·B2pin23 to aryl iodides and bromides is proposed based on these experimental observations.

Organo-Polyoxometalate-Based Hydrogen-Bond Catalysis.

Several urea-inserted organo-polyoxometalates (POMs) derived from polyoxotungstovanadate [P2 V3 W15 O61 ]9- were prepared. The insertion of the carbonyl into the polyoxometallic framework activates the urea toward Hydrogen-bond catalysis. This was shown on the Friedel-Crafts arylation of trans-ß-nitrostyrene. Modelling shows that the most stable form of the organo-POMs features a cis-trans arrangement of the two N-H bonds, but that the likely catalytically active trans-trans form is accessible at room temperature. Finally, it is possible that the oxo substituents next to the vanadium atoms may help the approach of the nucleophile via H-bonding.

Development of a Borane-(Meth)acrylate Photo-Click Reaction.

In the development of 3D printing fuels, there is a need for new photoinitiating systems working under mild conditions and/or leading to polymers with new and/or enhanced properties. In this context, we introduce herein N-heterocyclic carbene-borane complexes as reagents for a new type of photo-click reaction, the borane-(meth)acrylate click reaction. Remarkably, the higher bond number of boranes relative to thiols induced an increase of the network density associated with faster polymerization kinetics. Solid-state NMR evidenced the strong participation of the boron centers on the network properties, while DMA and AFM showed that the materials exhibit improved mechanical properties, as well as reduced solvent swelling.

Synthesis and Properties of Higher Nuclearity Polyazanes.

Polyazanes (i.e., higher nuclearity homologues of hydrazines) with increasing numbers of bound nitrogen atoms (from 3 to 5), including the first pentazane ever described, were prepared by the addition of lower-order polyazanes to diazo reagents. A structure was obtained. It was shown that the polynitrogen chains adopt a helical conformation. DFT modeling shows that the arrangement persists in solution. Although the polyazanes are all reducing agents, they become less so as the number of nitrogens increases.

Energetic Nitrogen-Rich Polymers with a Tetrazene-Based Backbone.

New energetic polymers were synthesized from monomers containing a trans-2-tetrazene unit. In contrast to traditional binders, such as inert hydroxytelechelic polybutadiene or glycidyl azide polymers-in which the energetic features are on the side chains-the energetic groups in the polytetrazenes are incorporated directly in the polymer backbone. Thermal analyses demonstrated that decomposition occurs at approximately 130 °C, regardless of the polymer structure. Glass-transition temperatures ranged from -34.2 to 0.2 °C and could be lowered further (to -61 °C) with the help of a new diazidotetrazene energetic plasticizer. Interestingly, hexafluoroisopropanol (HFIP) enabled complete, room-temperature depolymerization within 1 week. This depolymerization should enable the recycling of unused pyrotechnic compositions based on these new binders.

Solvent-free Synthesis and Properties of Functionalized Hydrazines and Bishydrazines as Energetic Ingredients for Propulsion Applications.

Functionalized hydrazines and bishydrazines are interesting straightforward precursors for accessing higher nitrogenated compounds. They offer structural diversity and promising energetic properties as well, namely for propulsion applications. A novel and scalable synthesis has been developed for a new family of bishydrazines, starting from monomethylhydrazine (MMH). This solvent-free route represents a suitable alternative to the one described in the literature. It was extended to design a new family of unsymmetrical hydrazines bearing various functional groups. A selected series of promising compounds, densified with nitrogenated groups (amino, hydrazino or azido functions), was identified as a class of plausible candidates for liquid propulsion. Indeed, the energetic interest of such hydrazines was demonstrated by computing their heats of formation and specific impulse values in bipropellant systems. This led to theoretical energetic performances comparable to that of the MMH/N2 O4 system already in use today.

Tunable Hydrogen Release from Amine-Boranes via their Insertion into Functional Polystyrenes.

Polystyrene-g-boramine random copolymers are dihydrogen reservoirs with tunable dehydrogenation temperatures, which can be adjusted by selecting the boramine content in the copolymers. They display a unique dihydrogen thermal release profile, which is a direct consequence of the insertion of the amine-boranes in a polymeric scaffold, and not from a direct modification of the electronics or sterics of the amine-borane function. Finally, the mixture of polystyrene-g-boramines with conventional NH3 -BH3 (borazane) allows for a direct access to organic/inorganic hybrid dihydrogen reservoirs with a maximal H2 loading of 8 wt %. These exhibit a dehydrogenation temperature lower than that of either the borazane or the polystyrene-g-boramines taken separately.

High Glass-Transition Temperature Polymer Networks Harnessing the Dynamic Ring Opening of Pinacol Boronates.

Differential scanning calorimetry of high molar mass poly(4-vinylphenylboronic acid, pinacol ester)s evidenced unusual reactive events above 120 °C, resulting in a high glass-transition temperature of 220 °C. A reversible ring-opening reactivity of pinacol boronates is proposed, involving a nucleophilic attack on the sp2 boron and subsequent bridging between boron atoms by interconnected pinacol moieties to form a densely crosslinked network with high Tg . FTIR, solid-state NMR investigations, and rheology studies on the polymer as well as double-tagging analyses on molecular model structures and theoretical calculations further support this hypothesis and indicate a ring-opening inducing crosslinking. When diluted in an apolar solvent such as toluene, the polymer network can be resolubilized via ring closing, thus recovering the entropically favored linear chains featuring cyclic boronate esters.

Thiolation of NHC-boranes: influence of the substitution at boron.

Several N-Heterocyclic Carbene (NHC)-boryl sulfides with B-substituents were prepared. The added steric hindrance leads to much improved selectivities as only the NHC-boryl mono-sulfides were obtained. The B-substituted NHC-boranes are also conducive to more selective S to N NHC-boryl shift, provided that the NHC used is not too sterically demanding.

Difluorination at Boron Leads to the First Electrophilic Ligated Boryl Radical (NHC-BF2. ).

1,3-Dimethylimidazol-2-ylidene difluoroborane (NHC-BF2 H) was prepared in a one-pot, two-step reaction from the parent ligated borane (NHC-BH3 ). The derived difluoroboryl radical (NHC-BF2. ) was generated by laser flash photolysis experiments and characterized by UV spectroscopy and rate-constant measurements. It is transient and reacts quickly with O2 . Unusually, it also reacts more rapidly with ethyl vinyl ether than with methyl acrylate. By this measure, it is the first electrophilic ligated boryl radical. Both NHC-BH3 and NHC-BF2 H serve as co-initiators in bulk photopolymerizations, converting both electron-poor and electron-rich monomers at roughly similar rates. However, the difluorinated coinitiator provides polymers with dramatically increased chain lengths from both monomers.

Visible-Light Emulsion Photopolymerization of Styrene.

The photopolymerization of styrene in emulsion is achieved in a conventional double-wall reactor equipped with a LED ribbon coiled around the external glass wall. Styrene mixed to acridine orange is added to the water phase containing sodium dodecyl sulfate, a water-soluble N-heterocyclic carbene-borane and disulfide, and irradiated. Highly stable latexes are obtained, with particles up to a diameter of 300 nm. The ability to reach such large particle sizes via a photochemical process in a dispersed medium is due to the use of visible light: the photons in the visible range are less scattered by larger objects and thus penetrate and initiate better the polymerizations. They are also greener and cheaper to produce via LEDs, and much safer than UVs. The method presented does not require any specific glassware; it works at lower temperature and delivers larger particles compared to thermal processes at similar solids contents and surfactant concentrations.

A Solid Iridium Catalyst for Diastereoselective Hydrogenation.

An Ir(NHC) supported catalyst is used in the selective hydrogenation of terpinen-4-ol to cis p-menthan-4-ol. Its activity, selectivity and stability are compared to those of a homogeneous homologue [IrCl(COD)MesImPr] and to a commercial Pd/C. The solid Ir catalyst is much more selective than the Pd catalyst (92 vs. 42 % at 80 °C) but also more active, more selective and more stable than the iridium complex in solution. For the first time, a supported catalyst shows an enhanced activity with respect to a complex in a diastereoselective hydrogenation reaction.

Elucidation of the Conformation of Polyglycine Organo-Polyoxotungstates: Evidence for Zipper Folding.

The conformation of a family of α1 and α2 polyglycine-containing organo-polyoxometalates was determined through a mixed experimental/molecular dynamics approach. The flexible peptide arm folds around the metal oxide surface in a rigid arrangement in low to average polarity solvents. The topology of the hybrid is the main factor that determines which oxos from the metal-oxide surface accept a H-bond from the closest amino acid. The rest of the peptide follows in a zipper mechanism that establishes a H-bond network that locks the system. The covalent constraint leads to a new type of H-bond where two consecutive amino acids clamp down terminal oxo ligands.

(E)-1,1,4,4-Tetramethyl-2-tetrazene (TMTZ): A Prospective Alternative to Hydrazines in Rocket Propulsion.

1,1,4,4-Tetramethyl-2-tetrazene (TMTZ) is considered as a prospective replacement for toxic hydrazines used in liquid rocket propulsion. The heat of formation of TMTZ was computed and measured, giving values well above those of the hydrazines commonly used in propulsion. This led to a predicted maximum Isp of 337 s for TMTZ/N2 O4 mixtures, which is a value comparable to that of monomethylhydrazine. We found that TMTZ has a vapor pressure well below that of liquid hydrazines, and it is far less toxic. Finally, an improved synthesis is proposed, which is compatible with existing industrial production facilities after minor changes. TMTZ is thus an attractive liquid propellant candidate, with a performance comparable to hydrazines but a lower vapor pressure and toxicity.

Grafting of Secondary Diolamides onto [P2 W15 V3 O62 ](9-) Generates Hybrid Heteropoly Acids.

The Dawson tungstovanadate [P2 W15 V3 O62 ](9-) can be grafted to secondary diolamides. The electron-withdrawing character of the polyanion increases the acidity of the amide proton, leading to an organo-polyoxometalate, which can be used as a Brønsted organocatalyst. High-field NMR and DFT modeling indicate that the amide proton stays on the nitrogen and that the exalted acidity derives from the interaction between the organic and inorganic parts of the organo-polyoxometalate. The amide-inserted vanadotungstates thus form a new family of (hybrid) heteropolyacids, offering new perspectives for the application of POM-based catalysis in organic synthesis.

Temperature Response of Rhodamine B-Doped Latex Particles. From Solution to Single Particles.

Nanoparticle-based temperature imaging is an emerging field of advanced applications. Herein, the sensitivity of the fluorescence of rhodamine B-doped latex nanoparticles toward temperature is described. Submicrometer size latex particles were prepared by a surfactant-free emulsion polymerization method that allowed a simple and inexpensive way to incorporate rhodamine B into the nanoparticles. Also, rhodamine B-coated latex nanoparticles dispersed in water were prepared in order to address the effect of the dye location in the nanoparticles on their temperature dependence. A better linearity of the temperature dependence emission of the rhodamine B-embedded latex particles, as compared to that of free rhodamine B dyes or rhodamine B-coated latex particles, is observed. Temperature-dependent fluorescence measurements by fluorescent confocal microscopy on individual rhodamine B-embedded latex particles were found similar to those obtained for fluorescent latex nanoparticles in solution, indicating that these nanoparticles could be good candidates to probe thermal processes as nanothermometers.

Polymer-containing Organo-Polyoxometalate: Towards New Catalytic Object.

Polyoxometalates (POMs) are early transition metal oxide clusters, which form a diverse family of compounds with highly tunable shapes, sizes, charges, etc. Generating hybrid structures is an attractive path to increase the structural diversity of POMs. The present article is a personal account that retraces how we inserted polyoxometallic platforms onto polymeric chains. We focused on two main families of functionalized organo-POMs: the organotin-substituted Dawson polyoxotunstates α1 and α2-[P(2)W(17)O(61)(SnR)](7-) and the Dawson vanadotungstates [P(2)V(3)W(15)O(59){(OCH(2))(2)-C(Et)NHC(=O)R}](5-). Herein we discuss how the connection of POMs to polymers affects the self-assembly of the polymers and the catalytic properties of the polyoxometalates.