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Dialkylmagnesium compounds (MgR2, R = C2H5, C4H9 etc.,) have drawn considerable interest in recent years due to their role in commercial polymerization reactions. Herein, we report a thorough account on the reaction intermediates involved in the synthesis of di-n-butylmagnesium from anhydrous magnesium chloride and n-butyllithium. Energy-dispersive X-ray spectroscopy (EDX) and powder X-ray diffraction (PXRD) were used to characterize the products formed in transmetalation reaction and it supports that the Schlenk equilibrium between the nBuMgCl and nBu2Mg may be operating during the synthesis of di-n-butylmagnesium from anhydrous magnesium chloride. 1,4-Dioxane was used to shift the Schlenk equilibrium to form soluble 1,4-dioxane adduct of di-n-butylmagnesium and insoluble MgCl2 based product. PXRD was used to study the transformation of 1,4-dioxane adduct of di-n-butylmagnesium to pure di-n-butylmagnesium.

Mass transfer coefficients of CO2 are anomalously high in water-lean solvents as compared to aqueous amines. Such phenomena are intrinsic to the molecular and nanoscale structure of concentrated organic CO2 capture solvents. To decipher the connections, we performed in situ liquid time-of-flight secondary ionization mass spectroscopy on a representative water-lean solvent, 1-((1,3-Dimethylimidazolidin-2-ylidene)amino)propan-2-ol (IPADM-2-BOL). Two-dimensional (2D) and three-dimensional (3D) chemical mapping of the solvent revealed that IPADM-2-BOL exhibited a heterogeneous molecular structure with regions of CO2-free solvent coexisting with clusters of zwitterionic carbonate ions. Chemical mapping were consistent with molecular dynamic simulation results, indicating CO2 diffusing through pockets and channels of unreacted solvent. The observed mesoscopic structure promotes and enhances the diffusion and reactivity of CO2, likely prevalent in other water-lean solvents. This finding suggests that if the size...

A new efficient and solvent-free method for the synthesis of anhydrous MgCl2 from its hexahydrate is presented. Fluidized dehydration of MgCl2·6H2O feedstock at 200 °C in a porous bed reactor yields MgCl2·nH2O (0 < n < 1), which has a similar diffraction pattern as activated MgCl2. The MgCl2·nH2O is then ammoniated directly using liquefied NH3 in the absence of solvent to form MgCl2·6NH3. Calcination of the hexammoniate complex at 300 °C then yields anhydrous MgCl2. Both dehydration and deammoniation were thoroughly studied using in situ as well as ex situ characterization techniques. Specifically, a detailed understanding of the dehydration process was monitored by in situ PXRD and in situ FTIR techniques where formation of salt with nH2O (n = 4, 2, 1

Addition of high pressures of H2 to five-coordinate [(tBu)4(POCOP)Ir(CO)(H)]OTf [(tBu)4(POCOP) = κ3-C6H3-2,6-(OP(tBu)2)2] complexes results in observation of two new iridium–dihydrogen complexes. If the aryl moiety of the POCOP ligand is substituted with an electron withdrawing protonated dimethylamino group at the para position, hydrogen coordination is enhanced. Five-coordinate Ir–H complexes generated by addition of triflic acid to (tBu)4(POCOP)Ir(CO) species show an Ir–H 1H NMR chemical shift dependence on the number of equivalents of acid present. It is proposed that excess triflic acid in solution facilitates triflate dissociation from iridium, resulting in unsaturated five-coordinate Ir–H complexes. The five-coordinate iridium–hydride complexes were found to catalyze H/D exchange between H2 and CD3OD. The existence of the dihydrogen complexes, as well as isotope exchange reactions, provide evidence for proposed ionic hydrogenation intermediates for glycerol deoxygenation.

This experimental and theoretical study investigates how dynamic solvation environments in switchable ionic liquids regulate the composition of nanoparticulate green rust. A custom microfluidic device enables in situ X-ray absorption spectroscopy to elucidate characterization of the solvent structure and speciation of reaction intermediates of air-sensitive nanoparticles growing in solution.

© 2017 the Owner Societies. Switchable ionic liquids (SWILs) derived from organic bases and alcohols are attractive due to their applications in gas capture, separations, and nanomaterial synthesis. However, their exact solvent structure still remains a mystery. We present the first chemical mapping of a SWIL solvent structure using in situ time-of-flight secondary ion mass spectrometry. In situ chemical mapping discovers two coexisting liquid phases and molecular structures vastly different from conventional ionic liquids. SWIL chemical speciation is found to be more complex than the known stoichiometry. Dimers and ionic clusters have been identified in SIMS spectra; and confirmed to be the chemical species differentiating from non-ionic liquids via spectral principal component analysis. Our unique in situ molecular imaging has advanced the understanding of SWIL chemistry and how this "heterogeneous" liquid structure may impact SWILs' physical and thermodynamic properties and associated applications.

In situ liquid secondary ion mass spectrometry (SIMS) enabled by system for analysis at the liquid vacuum interface (SALVI) has proven to be a promising new tool to provide molecular information at solid-liquid and liquid-vacuum interfaces. However, the initial data showed that useful signals in positive ion spectra are too weak to be meaningful in most cases. In addition, it is difficult to obtain strong negative molecular ion signals when m/z>200. These two drawbacks have been the biggest obstacle towards practical use of this new analytical approach. In this study, we report that strong and reliable positive and negative molecular signals are achievable after optimizing the SIMS experimental conditions. Four model systems, including a 1,8-diazabicycloundec-7-ene (DBU)-base switchable ionic liquid, a live Shewanella oneidensis biofilm, a hydrated mammalian epithelia cell, and an electrolyte popularly used in Li ion batteries were studied. A signal enhancement of about two orders of magnitude was obtained in comparison with non-optimized conditions. Therefore, molecular ion signal intensity has become very acceptable for use of in situ liquid SIMS to study solid-liquid and liquid-vacuum interfaces. Graphical Abstract ᅟ.

Three water adsorption-desorption mechanisms are common in inorganic materials: chemisorption, which can lead to the modification of the first coordination sphere; simple adsorption, which is reversible; and condensation, which is irreversible. Regardless of the sorption mechanism, all known materials exhibit an isotherm in which the quantity of water adsorbed increases with an increase in relative humidity. Here, we show that carbon-based rods can adsorb water at low humidity and spontaneously expel about half of the adsorbed water when the relative humidity exceeds a 50-80% threshold. The water expulsion is reversible, and is attributed to the interfacial forces between the confined rod surfaces. At wide rod spacings, a monolayer of water can form on the surface of the carbon-based rods, which subsequently leads to condensation in the confined space between adjacent rods. As the relative humidity increases, adjacent rods (confining surfaces) in the bundles are drawn closer together via capillary forces. At high relative humidity, and once the size of the confining surfaces has decreased to a critical length, a surface-induced evaporation phenomenon known as solvent cavitation occurs and water that had condensed inside the confined area is released as a vapour.

Switchable ionic liquids (SWIL) play an important role in green chemistry. Due to the nature of SWIL chemistry, such as air sensitivity, pressure, and temperature dependence, it is difficult to characterize SWIL using vacuum-based surface techniques. The fully CO2 loaded 1:1 mixtures of 1,8-diazabicycloundec-7-ene (DBU) and 1-hexanol (a SWIL system) and non-CO2 loaded DBU and 1-hexanol mixture were analyzed by in situ time-of-flight secondary ion mass spectrometry (ToF-SIMS) coupled with the system for analysis at the liquid vacuum interface (SALVI), respectively. The DBU/1-hexanol/CO2 SWIL was injected into the microchannel before liquid secondary ion mass spectrometry analysis. Bi3+ primary ion beam was used. The positive and negative spectra of the SWIL chemical components are presented. The characteristic peaks m/z 153 (protonated DBU) in the positive mode and m/z 101 (deprotonated 1-hexanol) in the negative mode were observed. In addition, ion pair peaks including m/z 253, 319, 305, and 451 in the po...

Mass transfer coefficients of CO

Combining CO2 capture and reduction is an efficient strategy to alleviate the high energy requirements for processing CO2 prior to reduction. Catalytic hydrogenation of CO2 captured as alkylcarbonate has previously been reported, but it's ambiguous whether the alkylcarbonate is reduced, as it is in dynamic equilibrium with neutral CO2 in solution. New studies are presented to elucidate the reduction mechanisms of CO2, and CO2 that is captured in solution using a homogeneous ruthenium hydride complex.