Synthesis of 2,6-Hexa-tert-butylterphenyl Derivatives, 2,6-(2,4,6-t-Bu3C6H2)2C6H3X, where X = I, Li, OH, SH, N3, or NH2.
ABSTRACT: A "double benzyne" reaction between 1,3-dichloro-2-iodobenzene and 2,4,6-t-Bu3C6H2MgBr followed by the addition of iodine led to 2,6-(2,4,6-t-Bu3C6H2)2C6H3I (HTBTI) in 65% yield. Lithiation of HTBTI with Li-t-Bu gave Li(Et2O)2HTBT from which HTBTSH, HTBTN3, HTBTNH2, and HTBTOH were prepared. An X-ray structure of W(OHTBT)2Cl4 shows that the two HTBTO ligands are trans to one another with the t-Bu3C6H2 groups on one HTBTO interdigitated with the t-Bu3C6H2 groups on the other HTBTO.
Project description:The ?-unsubstituted title compound dissolves in THF as a uniformly trisolvated monomer, whereas it forms exclusively disolvated monomers in tert-butyl methyl ether, Et2O, TMEDA, or toluene with TMEDA (1.4 equiv). This was established at low temperatures through the observation of separated NMR signals for free and lithium-coordinated ligands and/or through the patterns and magnitudes of (13)C,(6)Li NMR coupling constants. An aggregated form was observed only with Et2O (2 equiv) in toluene as the solvent. The olefinic geminal interproton coupling constants of the H2C= part can be used as a secondary criterion to differentiate between these differently solvated ground-states (3, 2, or <2 coordinated ligands per Li). Due to a kinetic trisolvation privilege of THF, the cis/trans sp(2)-stereoinversion rates could be measured through analyses of (1)H NMR line broadening and coalescence only in THF as the solvent: The pseudomonomolecular (because THF-catalyzed), ionic mechanism is initialized by a C-Li bond heterolysis with the transient immobilization of one additional THF ligand, followed by stereoinversion of the quasi-sp(2)-hybridized carbanionic center in cooperation with a "conducted tour" migration of Li(+)(THF)4 along the ?-aryl group within the solvent-separated ion pair.
Project description:Fluoroaromatic scaffolds pose a challenge to lithiation due to low stability of lithiated intermediates. Here we apply trans-metal-trapping (TMT) to a series of key fluorinated aromatics. In TMT, LiTMP performs the metalation, while an organometallic trap intercepts the emergent carbanion. This study contrasts the trapping abilities of iBu2 AlTMP and Ga(CH2 SiMe3 )3 , structurally mapping their TMT reactions and probing relative stabilities of metalated fluoroaromatic intermediates by NMR studies. Results show the installed Al-C(aryl) bonds are more prone to decomposition by benzyne formation and Li-F liberation, than the Ga-C(aryl) species. The latter are thus better for onward reactivity as demonstrated in cross-coupling reactions with benzoyl chloride that produce ketones.
Project description:The development of Li focused ion beams (Li-FIB) enables controlled Li ion insertion into materials with nanoscale resolution. We take the first step toward establishing the relevance of the Li-FIB for studies of ion dynamics in electrochemically active materials by comparing FIB lithiation with conventional electrochemical lithiation of isolated ?-Sn microspheres. Samples are characterized by cross-sectioning with Ga FIB and imaging via electron microscopy. The Li-FIB and electrochemical lithiated Sn exhibit similarities that suggest that the Li-FIB can be a powerful tool for exploring dynamical Li ion-material interactions at the nanoscale in a range of battery materials.
Project description:The rapid insertion and extraction of Li ions from a cathode material is imperative for the functioning of a Li-ion battery. In many cathode materials such as LiCoO2, lithiation proceeds through solid-solution formation, whereas in other materials such as LiFePO4 lithiation/delithiation is accompanied by a phase transition between Li-rich and Li-poor phases. We demonstrate using scanning transmission X-ray microscopy (STXM) that in individual nanowires of layered V2O5, lithiation gradients observed on Li-ion intercalation arise from electron localization and local structural polarization. Electrons localized on the V2O5 framework couple to local structural distortions, giving rise to small polarons that serves as a bottleneck for further Li-ion insertion. The stabilization of this polaron impedes equilibration of charge density across the nanowire and gives rise to distinctive domains. The enhancement in charge/discharge rates for this material on nanostructuring can be attributed to circumventing challenges with charge transport from polaron formation.
Project description:Silicon microwire arrays embedded in Cu present exceptional performance as anode material in Li ion batteries. The processes occurring during the first charging cycles of batteries with this anode are essential for good performance. This paper sheds light on the electrochemical and structural properties of the anodes during the first charging cycles. Scanning Electron Microscopy, X-ray diffractommetry, and fast Fourier transformation impedance spectroscopy are used for the characterization. It was found that crystalline phases with high Li content are obtained after the first lithiation cycle, while for the second lithiation just crystalline phases with less Li are observable, indicating that the lithiated wires become amorphous upon cycling. The formation of a solid electrolyte interface of around 250 nm during the first lithiation cycle is evidenced, and is considered a necessary component for the good cycling performance of the wires. Analog to voltammetric techniques, impedance spectroscopy is confirmed as a powerful tool to identify the formation of the different Si-Li phases.
Project description:4,6-Dihydroxysalicylic acid was activated under air to catalyze the one-pot oxidative condensation reaction of benzylamines with acetophenones in the presence of BF3·Et2O, affording 2,4,6-trisubstituted pyridines in yields of 59-91%. During this metal-free oxidative condensation reaction, the benzylamines not only provided the aryl moiety at the 4-position of the pyridines but also acted as the nitrogen donor. This method can be applied to the metal-free synthesis of G-quadruplex binding ligands by the sequential addition of 4-chlorobutyryl chloride and pyrrolidine to the reaction system of the 2,4,6-trisubstituted pyridine synthesis.
Project description:Sn2Fe anode materials were synthesized by a solvothermal route, and their electrochemical performance and reaction mechanism were evaluated. The structural evolution in the first two lithium cycles was investigated by X-ray absorption spectroscopy (XAS), synchrotron X-ray diffraction (XRD), and magnetic studies. In the first cycle, progressive alloying of Sn with Li accompanied by metallic iron displacement occurs upon lithiation, and the delithiation proceeds by Li x Sn dealloying and recovery of the Sn2Fe phase. In the second cycle, both XRD and XAS identify Li-Sn alloying at earlier lithiation stages than in the first cycle, with low-Li-content alloys evident in the beginning of the lithiation process. In the fully lithiated state, XAS analysis reveals higher coordination numbers in both the Li x Sn and Fe phases, which points toward more complete reaction and higher crystallinity of the products. Upon second delithiation, the Sn2Fe phase is generally reformed as evidenced by XRD. However, XAS indicates somewhat reduced Sn-Fe coordination and shorter Fe-Fe distance, which indicates incomplete reconversion and metallic Fe retention, which is also evident in the magnetic studies. Thus, a combination of long-range (XRD, magnetic) and local (XAS) techniques has revealed differences between the first and the second Li cycles relevant to the understanding of the capacity fading mechanisms.
Project description:Following an explosion of studies of silicon as a negative electrode for Li-ion batteries, the anomalous volumetric changes and fracture of lithiated single Si particles have attracted significant attention in various fields, including mechanics. However, in real batteries, lithiation occurs simultaneously in clusters of Si in a confined medium. Hence, understanding how the individual Si structures interact during lithiation in a closed space is necessary. Here, we demonstrate physical and mechanical interactions of swelling Si structures during lithiation using well-defined Si nanopillar pairs. Ex situ SEM and in situ TEM studies reveal that compressive stresses change the reaction kinetics so that preferential lithiation occurs at free surfaces when the pillars are mechanically clamped. Such mechanical interactions enhance the fracture resistance of lithiated Si by lessening the tensile stress concentrations in Si structures. This study will contribute to improved design of Si structures at the electrode level for high-performance Li-ion batteries.
Project description:In order to make fast-charging batteries a reality for electric vehicles, durable, more energy dense and high-current density resistant anodes need to be developed. With such purpose, a low lithiation potential of 0.2 V vs. Li/Li(+) for MoO3 nanoplatelet arrays is reported here for anodes in a lithium ion battery. The composite material here presented affords elevated charge capacity while at the same time withstands rapid cycling for longer periods of time. Li2MoO4 and Li(1.333)Mo(0.666)O2 were identified as the products of lithiation of pristine MoO3 nanoplatelets and silicon-decorated MoO3, respectively, accounting for lower than previously reported lithiation potentials. MoO3 nanoplatelet arrays were deposited using hot-wire chemical vapor deposition. Due to excellent voltage compatibility, composite lithium ion battery anodes comprising molybdenum oxide nanoplatelets decorated with silicon nanoparticles (0.3% by wt.) were prepared using an ultrasonic spray. Silicon decorated MoO3 nanoplatelets exhibited enhanced capacity of 1037 mAh g(-1) with exceptional cyclability when charged/discharged at high current densities of 10 A g(-1).
Project description:As opposed to the common understanding that diffusion into a cubic-structured single crystal is independent of its crystalline orientation, the diffusion of Li to crystalline Si (c-Si) is anisotropic, which acts as the major cause for the fracture of Si anodes in Li-ion batteries. Here, by conducting comprehensive/multi-scale simulation studies based on molecular dynamics and density functional theory, we elucidate how and why Li diffusion in c-Si is anisotropic. We found that Li ions diffuse to c-Si by following a particular atomic-scale space corresponding to the lowest value of the valence orbital in c-Si, causing Li ions to take a tortuous diffusion pathway. The degree of the tortuosity of the pathway differs depending on the crystallographic orientation of Si, and it acts as the major cause for anisotropic lithiation. We also develop a structural parameter that can quantitatively evaluate the orientation dependency of the lithiation of c-Si.