29Si Nuclear Magnetic Resonance Research Articles

Aluminum Alkyl Induced Isomerization of Group IV meso Metallocene Complexes

The synthesis of group IV metallocene precatalysts for the polymerization of propylene generally yields two different isomers: The racemic isomer that produces isotactic polypropylene (iPP) and the meso isomer that produces atactic polypropylene (aPP). Due to its poor physical properties, aPP has very limited applications. To avoid obtaining blends of both polymers and thus diminish the mechanical and thermal properties of iPP, the meso metallocene complexes need to be separated from the racemic ones tediously –rendering the metallocene‐based polymerization of propylene industrially far less attractive than the Ziegler/Natta process. To overcome this issue, we established an isomerization protocol to convert meso metallocene complexes into their racemic counterparts. This protocol increased the yield of iPP by 400% while maintaining the polymer’s excellent physical properties and was applicable to both hafnocene and zirconocene complexes, as well as different precatalyst activation methods. Through targeted variation of the ligand frameworks, methoxy groups at the indenyl moieties were found to be the structural motifs responsible for an isomerization to take place –this experimental evidence was confirmed by density functional theory calculations. Liquid injection field desorption ionization mass spectrometry, as well as 1H and 29Si nuclear magnetic resonance studies, allowed the proposal of an isomerization mechanism.

Aluminum Alkyl Induced Isomerization of Group IV meso Metallocene Complexes.

The synthesis of group IV metallocene precatalysts for the polymerization of propylene generally yields two different isomers: The racemic isomer that produces isotactic polypropylene (iPP) and the meso isomer that produces atactic polypropylene (aPP). Due to its poor physical properties, aPP has very limited applications. To avoid obtaining blends of both polymers and thus diminish the mechanical and thermal properties of iPP, the meso metallocene complexes need to be separated from the racemic ones tediously -rendering the metallocene-based polymerization of propylene industrially far less attractive than the Ziegler/Natta process. To overcome this issue, we established an isomerization protocol to convert meso metallocene complexes into their racemic counterparts. This protocol increased the yield of iPP by 400% while maintaining the polymer's excellent physical properties and was applicable to both hafnocene and zirconocene complexes, as well as different precatalyst activation methods. Through targeted variation of the ligand frameworks, methoxy groups at the indenyl moieties were found to be the structural motifs responsible for an isomerization to take place -this experimental evidence was confirmed by density functional theory calculations. Liquid injection field desorption ionization mass spectrometry, as well as 1H and 29Si nuclear magnetic resonance studies, allowed the proposal of an isomerization mechanism.

Cosolvent-free sol–gel synthesis of macroporous silica gels from tetramethoxysilane–tetraethoxysilane mixtures

Abstract Tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and their mixtures were used for the cosolvent-free synthesis of macroporous silica gels as precursors for monolithic silica glasses. The liquid-state 29Si nuclear magnetic resonance (NMR) spectroscopy of precursor solutions indicated that cross-transesterification between TMOS and TEOS was completed in a few hours at 20 °C in the presence of an acid catalyst, whereas it was negligible when the catalyst was absent. In the precursor solutions prepared from TMOS, phase separation occurred after gelation, resulting in translucent gels. In contrast, in the solutions prepared from TEOS or a mixture of TMOS and TEOS at a TMOS mole fraction of 0.8, the phase separation can be induced before gelation, and opaque xerogels were easily obtained without fracture. The average size of macroscopic particles and macroporous structures were uniform over opaque xerogels prepared from TEOS. In contrast, in opaque xerogels prepared from the TMOS-rich mixture of TMOS and TEOS, the average particle size and macroscopic porosity inside them were notably smaller than those of the subsurface, probably because of a large exotherm upon gelation and the resulting temperature gradient in the gelling solutions. Such spatial morphology distribution made the sintering of the opaque gels into clear silica glasses difficult. Opaque gels prepared from TEOS and translucent gels prepared from solutions containing TMOS were transformed to clear silica glasses in high yields of ~99% by sintering in a helium atmosphere at 1050–1350 °C. Graphical abstract

Atomistic origin of structural relaxation in lead metasilicate and lithium disilicate glasses

AbstractA combination of density measurement, differential scanning calorimetry, refractometry, and Raman and 29Si nuclear magnetic resonance (NMR) spectroscopy is employed to characterize the evolution of the structure and physical properties of lithium disilicate (Li2Si2O5) and lead metasilicate (PbSiO3) glasses during physical aging. Both glasses display marked increase in density, enthalpy recovery, and refractive index following a temperature down‐jump near their glass transition regions. The collective analysis of Raman and NMR spectra reveals that the aging‐induced structural relaxation in these silicate networks involves a significant disproportionation of Q‐species as well as their spatial clustering.

Monitoring the Geopolymerization Reaction of Geopolymer Foams Using 29Si and 27Al MAS NMR

This study aims to investigate the geopolymerization reaction of geopolymer foams produced with three different foaming agents: aluminum powder, zinc powder, and hydrogen peroxide. The geopolymerization reaction of geopolymer foam was monitored using the 27Al and 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy technique. 27Al MAS-NMR was used to monitor the reaction at an early stage, while 29Si and 27Al MAS-NMR analyses were employed at specific time intervals of 3, 6, 10, 15, and 28 days to examine the changes that occurred in the formed gel over time. We discussed in detail how the type of foaming agent used and the duration of the reaction both influence the quantity of gel formed and the amount of remnant fly ash. Our findings indicate that the type of foaming agent used affects the formation and structure of the gel, with aluminum powder leading to the highest gel formation. Additionally, the duration of the reaction plays a significant role in determining the quantity of remnant fly ash, with longer reaction times resulting in decreased fly ash content. This study sheds light on the relevance of understanding the role of foaming agents in the geopolymerization reactions of geopolymer foams and the influence of reaction time on the formed gel properties.

Influences of composition and reaction conditions on molecular structure, hygroscopicity, and swelling behavior of alkali-silica reaction gels

Alkali-silica reaction (ASR) gel, a product of the reactions between the dissolved silica from aggregate and the alkalis from cement, governs the destructiveness of ASR and concrete deterioration. The influences of chemical composition and reaction conditions of ASR gel on its structure and properties remain unclear. In this work, the correlations between the molecular structure, hygroscopicity, and swelling behavior of ASR products were uncovered by investigating six CaO–SiO2-M2O systems with varying alkali/Si and Ca/Si ratios under two reaction conditions. The results indicate that the low-alkali gels have a layered silicate structure dominated by Q1 and Q2 sites similar to calcium silicate hydrate (C–S–H), whereas the high-alkali gels showed coexistence of tobermorite-type C–S–H and alkali-silicate hydrates featured with Q3 polymerization. The 29Si nuclear magnetic resonance (NMR) results showed that the mean chain length (MCL) and degree of polymerization (DP) decrease with alkali/Si and Ca/Si ratios but increase with moisture. Under 97 % RH, decreased crystallinity and enhanced formation of ASH and Q3 sites are obtained along with increased polymerization and d-spacing. The moisture uptake and swelling of the high-alkali gels showed a reverse correlation with the Ca/Si ratio, which confirms the role of calcium in suppressing the formation of ASH and the dominant role of Q3 sites in determining the hygroscopicity of ASR products.

The influence of carbon dioxide concentration on carbonation behavior in cement paste

Accelerated carbonation is the main method of simulating carbonation in the laboratory, but there are significant differences in the CO2 concentrations adopted for accelerated carbonation testing among the various standards currently. In this work, X-ray imaging technology was used to study the distribution of the carbonation zone in samples at different CO2 concentrations and used for imaging, which was followed by quantitative analyses of the carbonation profile and the material compositions of the entire carbonation zone in combination with thermogravimetric analysis (TGA) and 29Si nuclear magnetic resonance (29Si NMR) analyses. The results showed that the carbonation profiles of cement paste were similar under 3% and 10% concentration, with the front line of carbonation developing parallel to the soffit of the sample. However, when the concentration was increased to 20%, the carbonation profile at partial carbonation zone could be changed due to shrinkage cracking. In addition, the compositions of the complete carbonation zone under different concentrations were similar, and the development of this zone followed Fick's law.

Insights into microstructural alterations in alkali-activated materials incorporating municipal solid waste incineration fly ash

Municipal solid waste incineration fly ash (MSWI FA) is categorized as a hazardous waste with significant implications on environmental safety and human health. This study tailored three types of alkali-activated materials (AAMs) by using ground granulated blast-furnace slag (GGBS) and metakaolin (MK) for the low-carbon stabilization/solidification (S/S) of MSWI FA. The intricate interactions between MSWI FA and AAMs synthesized from Al-rich precursors and Ca-rich precursors were investigated to elucidate the microstructural alterations of AAM-MSWI FA systems. Comprehensive characterization techniques were conducted, including isothermal calorimeter, thermal gravimetric analysis, Fourier-transform infrared (FTIR), X-ray diffraction (XRD), and 27Al and 29Si nuclear magnetic resonance (NMR). The results revealed that the incorporation of MSWI FA significantly delayed alkali activation reactions, hindering the formation of aluminosilicate gel due to high contents of Cl and potentially toxic elements (PTEs) in the MSWI FA. High volume of dissolved Cl from MSWI FA would react with available Ca from MSWI FA and GGBS as well as Al from GGBS and MK to form Friedel’s salt, and this reaction was found to be more dominant in the Al-rich environment. Meanwhile, the C-(N-)A-S-H gel exhibited longer chain length in the Al-rich environment than in the Ca-rich environment. Overall, this study delivers microstructural insights into AAM-MSWI FA systems utilizing GGBS and MK as precursors. The results provide scientific groundwork for diverse practical applications of AAM-MSWI FA materials, thereby supporting the development of resource-efficient and low-carbon hazardous waste treatment strategies.

Investigation on the early proceeding of cement hydration containing dispersed nano Calcium Silicate Hydrated (CSH) seeds

Steam curing process is a traditional method for accelerating the progression of cement hydration to satisfy the rapid development of compressive strength in precast concrete industry. However, steam curing would release significant amount of CO2 into the atmosphere. In order to avoid the serious environmental pollution caused by the steam curing process, Calcium Silicate Hydrate (CSH) dispersed by comb-like polycarboxylate superplasticizer (PCE), shorted as dispersed nano CSH seed, was utilized to promote the early cement hydration at normal temperature. This investigation aims at disclosing the hydration process of cement and the microstructure evolution of cement paste in the presence of dispersed nano CSH seed during the early stage via setting time, ultrasonic pulse velocity (UPV), compressive strength, conductivity, pH, thermogravimetric (TG), 29Si NMR and nitrogen adsorption/desorption. The results demonstrated that with the dispersed nano CSH seed increasing, the setting process of cement paste was shortened dramatically, the compressive strength and UPV of cement mortar increased significantly especially at 12 h. The variation of conductivity and pH of cement suspension indicated that the ion dissolution process was promoted by dispersed nano CSH seed, which therefore conducive to the precipitation of cement hydration products. TG curves exhibited that the formation of cement hydration products, including CH (Calcium Hydrated), AFt and CSH gel were accelerated by dispersed nano CSH seed. The 29Si NMR (Nuclear Magnetic Resonance) and nitrogen adsorption/desorption results validated that the incorporating dispersed nano CSH seed promoted considerably the polymerization of CSH gel. The aforementioned results are correlated well with the fast formation of microstructure and in turn the rapid development of compressive strength at early age.

Exploring the potential of pulverized oyster shell as a limestone substitute in limestone calcined clay cement (LC3) and its implications for performance

With the advent of rapid climate change and global warming, the cement industry has been actively striving to minimize its carbon footprint. An effective approach for reducing carbon emissions is to utilize supplementary cementitious materials (SCMs). Limestone calcined clay cement (LC3) has garnered significant attention because of its ability to reduce clinker use by approximately 45 wt%, compared to ordinary Portland cement. However, the raw materials involved in LC3 production, which are obtained through mining and heating of raw clay, also counts toward the carbon footprint. Therefore, the present study aims to explore the feasibility of using oyster shells as a replacement for limestone in LC3 systems. Various amorphousness of calcined clay were tested to investigate the hydration reaction and strength of the oyster shell calcined clay cement (OC3). Data collected using techniques such as X-ray diffraction, thermogravimetry, scanning electron microscopy, isothermal calorimetry, compressive strength testing, and 29Si nuclear magnetic resonance spectroscopy were analyzed to elucidate the hydration reaction mechanisms of OC3, considering the type of calcite (oyster shell or limestone) and the extent of the transformation of kaolinite clay to metakaolin. The findings of this study demonstrate that oyster shells can effectively replace limestone as a raw material for LC3. Furthermore, the irregular morphology of the shell particles enhanced the hydration reaction and development of the cement’s microstructure.

Zn(II) loaded silylated bentonites as antibacterial materials: Influence of the surface functionalization

Antimicrobial materials based on metal cations loaded on solids have been widely investigated against different bacteria. In this study, sodium bentonite was silylated in the presence of different organosilanes containing one, two or three nitrogen atoms. Reactions were performed, free of solvent, under microwave irradiation at 50 °C and 5 min. Raw and silylated solids were loaded with Zn(II) cations, and their antibacterial activities against Staphylococcus aureus and Escherichia coli were evaluated. The obtained silylated samples were characterized using X-ray diffraction, Fourier transform infrared spectroscopy (FT-IR), 13C and 29Si nuclear magnetic resonance (NMR), zeta potential measurements, CHN elemental analysis, scanning electron microscopy (SEM), transmission electron microscopy, and thermogravimetric analysis. Silanes were successfully covalently bonded to the silanols of the clay mineral and intercalated, resulting in an increase in the basal space. Antibacterial testing of the Zn2+ loaded solids revealed a maximum inhibition of up to 88 % and 62 % of both the bacteria Staphylococcus aureus and Escherichia coli.

Geopolymers made using organic bases. Part I: Synthesis and atomic structure

AbstractGeopolymers can act as a facile forming route to aluminosilicate ceramic composites due to being processed as fluids rather than as powders. However, the compositions available via typical alkali geopolymers are limited by the presence of alkali cations, introduced by the alkali silicate solution precursors. In order to expand the ceramic compositions that are accessible by geopolymer processing, this study explored the use of three strong organic bases (guanidine, tetramethylguanidine [TMG], and tetramethylammonium hydroxide [TMAOH]) as alternatives to inorganic alkali hydroxides in geopolymer synthesis. Silicate solutions were able to be produced with all three bases and favorable silica speciation was identified in the guanidine and TMG silicate solutions. Monolithic bodies were produced using guanidine and TMAOH, while no TMG samples hardened. By 27Al and 29Si nuclear magnetic resonance spectroscopy and powder X‐ray diffraction, the guanidine samples were determined to be structurally similar to those made using sodium hydroxide and hence can be called geopolymers, while the solids made with TMAOH were not structurally similar to sodium geopolymers and contained one or more unknown phases. This study has demonstrated that geopolymers can be made using organic bases rather than alkali hydroxides and that the speciation of dissolved silica alone does not indicate that an organic base silicate solution will be reactive.

TS-1@MCM-48 Core-Shell Catalysts for Efficient Oxidation of p-Diethylbenzene to High Value-Added Derivatives.

To expand the market capacity of p-diethylbenzene (PDEB), core-shell zeolite (TS-1@MCM-48) is designed as a catalyst for PDEB oxidation. TS-1@MCM-48 catalyst is synthesized by in-situ crystallization method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), N2 adsorption-desorption, in-situ electron paramagnetic resonance (EPR) and 29Si nuclear magnetic resonance (29Si MAS-NMR). Oxidation of PDEB by H2O2 was investigated systematically in liquid phase. The conversion of PDEB over TS-1@MCM-48 was 28.1 % and the total selectivity was 72.6 %, where the selectivity of EAP (p-ethylacetophenone) and EPEA (4-ethyl-α-methylbenzyl alcohol) was 28.6 % and 44.0 %, respectively. Compared with TS-1 and MCM-48 zeolite, the conversion rate of reactants and the selectivity of products have been significantly improved. The catalytic performance of TS-1@MCM-48 is derived from its well-crystallized microporous core and mesoporous shell with regular channels, which make active sites of TS-1 zeolite in the catalyst be fully utilized and mass transfer resistance be largely reduced. Further through theoretical calculation, we propose that the oxidation of PDEB is the result of the combination and mutual transformation of free radical process and carbocation process. Core-shell structure ensures the conversion rate of raw materials and improves the selectivity of products.

Catalytic Cracking of 1,3,5‐Triisopropylbenzene and Low‐Density Polyethylene over Hierarchical Y Zeolites and Al‐SBA‐15

AbstractCatalytic cracking of high molecular weight hydrocarbons underpins the production of fossil fuels from petroleum vapour and the recycling of polyolefin waste plastic. However, thermal cracking over conventional microporous solid acids is hindered by poor mass‐transport. Here we explore the performance of hierarchical H−Y zeolites and Al‐SBA‐15 for the catalytic cracking of 1,3,5‐triisopropylbenzene (1,3,5‐TIPB) and low‐density polyethylene (LDPE) in a continuous fixed‐bed flow reactor. Dealumination by acid washing was used to create hierarchical mesoporosity in H−Y zeolite and modify the solid acidity. Physicochemical properties were studied by X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), gas adsorption, in‐situ Fourier transform infrared (FTIR), ex‐situ pyridine DRIFT, 29Si and 27Al nuclear magnetic resonance (NMR), and 1H relaxation and pulsed field gradient (PFG) NMR diffusion studies. Despite weakening acidity, the introduction of hierarchical porosity promotes deep cracking of both feedstocks; HNO3 dealuminated H−Y produces five times more cumene and benzene from 1,3‐5‐TIPB, and 33 % more benzene and xylenes from LDPE, than the parent H−Y.

Influence of monomer concentration on structures of fully condensed polyphenylsilsesquioxanes

Fully condensed polyphenylsilsesquioxanes have been prepared via the hydrolysis and condensation of the same phenyltrimethoxysilane (PTMS) monomer in different concentrations. The effect of monomer concentration on molecular structure of the final products has been thoroughly investigated. Cage structured polyphenylsilsesquioxane (OPS) and ladder-like structured polyphenylsilsesquioxane (L-PPSQ) can be selectively synthesized from the same starting materials at lower and higher initial monomer concentrations. Meanwhile, online infrared detector, React IR TM15 was used to monitor the real time variation of the concentration and characteristic absorption peaks of any intermediate products that may exist. Then, React IR TM15 coupled with 29Si nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS) were used to monitor and identify the intermediate species during the reaction. Mechanism studies indicated that the condensation reaction of OPS and L-PPSQ both proceed through a T1 structure dimer, which was formed by the quick hydrolysis of the PTMS monomer. As confirmed by 29Si-NMR, GPC and MALDI-TOF-MS, the synthesis mechanisms of OPS and L-PPSQ during the hydrolysis-condensation reactions were delineated.

Advanced Anticorrosive Graphene Oxide-Doped Organic-Inorganic Hybrid Nanocomposite Coating Derived from Leucaena leucocephala Oil.

Metal corrosion poses a substantial economic challenge in a technologically advanced world. In this study, novel environmentally friendly anticorrosive graphene oxide (GO)-doped organic-inorganic hybrid polyurethane (LFAOIH@GO-PU) nanocomposite coatings were developed from Leucaena leucocephala oil (LLO). The formulation was produced by the amidation reaction of LLO to form diol fatty amide followed by the reaction of tetraethoxysilane (TEOS) and a dispersion of GOx (X = 0.25, 0.50, and 0.75 wt%) along with the reaction of isophorane diisocyanate (IPDI) (25-40 wt%) to form LFAOIH@GOx-PU35 nanocomposites. The synthesized materials were characterized by Fourier transform infrared spectroscopy (FTIR); 1H, 13C, and 29Si nuclear magnetic resonance; and X-ray photoelectron spectroscopy. A detailed examination of LFAOIH@GO0.5-PU35 morphology was conducted using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy. These studies revealed distinctive surface roughness features along with a contact angle of around 88 G.U preserving their structural integrity at temperatures of up to 235 °C with minimal loading of GO. Additionally, improved mechanical properties, including scratch hardness (3 kg), pencil hardness (5H), impact resistance, bending, gloss value (79), crosshatch adhesion, and thickness were evaluated with the dispersion of GO. Electrochemical corrosion studies, involving Nyquist, Bode, and Tafel plots, provided clear evidence of the outstanding anticorrosion performance of the coatings.

Reduce the cost and embodied carbon of ultrahigh performance concrete using waste clay

Recent research has recognized limestone calcined clay cement (LC3) a promising sustainable cementitious material. While LC3 could be used in a wide range of applications, it is important to explore its feasibility in developing (ultra-)high performance concrete. In this paper we attempt to produce ultrahigh performance LC3 concrete (UHP-LC3). With 20%, 30%, and 40% OPC replaced by coal gangue waste calcined clay and limestone (LC2), the mechanical, hydration, and microstructural properties were extensively studied. The mechanical properties were investigated by compressive and flexural tensile tests. The hydration behavior of UHP-LC3 was evaluated by thermogravimetric analysis (TGA), quantitative X-ray powder diffraction (QXRD) analysis, 29Si nuclear magnetic resonance (NMR) spectroscopy, and scanning electron microscope (SEM). Finally, the microstructure of UHP-LC3 was studied by mercury intrusion porosimetry (MIP). Results show that the substitution of LC2 improve the early strength by quickly pozzolanic reaction to form denser hydration products as well as the synergistic interaction between silica fume and limestone/calcined clay in the system. However, the long-term strength would drop as LC3 caused insufficient hydration reaction due to the high water-demand of calcined clay that reduced the amount of free water. Also, there are abundant unreacted calcined clay particles in the hydrated system. Meanwhile, LC3 substitution of OPC seems to improve the polymerization of C-A-S-H gel and densify the pore structure, thus display excellent carbonation resistance. This paper explores new options to prepare more sustainable and cost-effective UHPC.

Wettability, adhesive performance and structural evolution of an environment-friendly modified silicate binder for foundry moulding and coremaking

For the manufacturing of sand cores, silicate inorganic binders have emerged as promising green casting binder materials; however, their adhesive performance requires further improvement. In this study, to evaluate the impact of using water-soluble polyols, i.e. polyethylene glycol (PEG) and xylitol, to modify silicate adhesives, the effect of the content and type of water-soluble polyol on the colloidal stability, wettability and adhesive performance of a silicate binder were investigated. The structural evolution of the modified silicate binder and the polysilicate bondswere studied using characterisation techniques including infrared spectroscopy and 29Si nuclear magnetic resonance (NMR) spectroscopy. Results revealed that PEG 400 and PEG 600 increased the size of polysilicate particles in the solution, resulting in flocculation of the silicate binders and easy precipitation or separation in a short period of time. However, PEG 200 and xylitol exerted little effect on the stability of the silicate solution. Moreover, 0.25 wt% PEG 200 reduced the surface tension of the solution from 78.93 to 54.15 mN/m and the equilibrium contact angle from 45.0° to 34.6°. The polyol promoted the dehydration and condensation of silicic acid gel to form a more stable three-dimensional network structure, improving the bonding strength of casting sand cores prepared using the silicate binder and silica sand from 2.42 to 3.02 MPa. This study not only unveils the role of PEG in improving the wettability and bonding behaviour but also provides an example of the rational use of environment-friendly water-soluble polyols to enhance the performance of green inorganic adhesive materials.

ZrOsSi: a Z2 topological metal with a superconducting ground state

The silicide superconductors (Ta, Nb, Zr)OsSi are among the best candidate materials for investigating the interplay of topological order and superconductivity. Here, we investigate in detail the normal-state topological properties of (Ta, Nb, Zr)OsSi, focusing on ZrOsSi, by employing a combination of 29Si nuclear magnetic resonance (NMR) measurements and first-principles band-structure calculations. We show that, while (Ta, Nb)OsSi behave as almost ideal metals, characterized by weak electronic correlations and a relatively low density of states, the replacement of Ta (or Nb) with Zr expands the crystal lattice and shifts ZrOsSi towards an insulator. Our ab initio calculations indicate that ZrOsSi is a Z2 topological metal with clear surface Dirac cones and properties similar to a doped strong topological insulator.

Carbon-Nitrogen Bond Formation Using Sodium Hexamethyldisilazide: Solvent-Dependent Reactivities and Mechanisms.

The solvent-dependent reactivity of sodium hexamethyldisilazide (NaHMDS) toward carbon-centered electrophiles reveals reactions that are poorly represented or unrepresented in the literature, including direct aminolysis of aromatic methyl esters to give carboxamides, nitriles, or amidines, depending on the choice of solvent. SNAr substitutions of aryl halides and opening of terminal epoxides are also examined. A combination of 1H and 29Si nuclear magnetic resonance (NMR) spectroscopic studies using [15N]NaHMDS, kinetic studies, and computational studies reveals the complex mechanistic basis of the preferences for simple aryl carboxamides in toluene and dimethylethylamine and arylnitriles or amidines in tetrahydrofuran (THF). A prevalence of dimer- and mixed dimer-based chemistry even starting from the observable NaHMDS monomer in THF solution is notable.