RESUMO
Nickel's +1 oxidation state has received much interest due to its varied and often enigmatic behavior in increasingly popular catalytic methods. In part, the lack of understanding about NiI results from common synthetic strategies limiting the breadth of complexes that are accessible for mechanistic study and catalyst design. We report an oxidative approach using tribromide salts that allows for the generation of a well-defined precursor, [NiI(COD)Br]2, as well as several new NiI complexes. Included among them are complexes bearing bulky monophosphines, for which structure-speciation relationships are established and catalytic reactivity in a Suzuki-Miyaura coupling (SMC) is investigated. Notably, these routes also allow for the synthesis of well-defined monomeric t-Bubpy-bound NiI complexes, which has not previously been achieved. These complexes, which react with aryl halides, can enable previously challenging mechanistic investigations and present new opportunities for catalysis and synthesis.
RESUMO
The rise of virtual and online education in recent years has led to the development and popularization of many online tools, notably three-dimensional (3D) models and augmented reality (AR), for visualizing various structures in chemical sciences. The majority of the developed tools focus on either small molecules or biological systems, as information regarding their structure can be easily accessed from online databases or obtained through relatively quick calculations. As such, due to a lack of crystallographic and theoretical data available for nonbiological macromolecules, there is a noticeable lack of accessible online tools for the visualization of polymers in 3D. Herein, using a few sample polymers, we showcase a workflow for the generation of 3D models using molecular dynamics and Blender. The 3D structures can then be hosted on p3d.in, where AR models can be generated automatically. Furthermore, the hosted 3D models can then be shared via quick response (QR) codes and used in various settings without the need to download any applications.
RESUMO
The energetic disorder induced by fluctuating liquid environments acts in opposition to the precise control required for coherence-based sensing. Overcoming fluctuations requires a protected quantum subspace that only weakly interacts with the local environment. We report a ytterbium complex that exhibited an ultranarrow absorption linewidth in solution at room temperature with a full width at half maximum of 0.625 milli-electron volts. Using spectral hole burning, we measured an even narrower linewidth of 410 pico-electron volts at 77 kelvin. Narrow linewidths allowed low-field magnetic circular dichroism at room temperature, used to sense Earth-scale magnetic fields. These results demonstrated that ligand protection in lanthanide complexes could substantially diminish electronic state fluctuations. We have termed this system an "atomlike molecular sensor" (ALMS) and proposed approaches to improve its performance.
RESUMO
This is a comprehensive study of the effects of rationally designed hemilabile ligands on the stability, reactivity, and change in catalytic behavior of indium complexes. We report cationic alkyl indium complexes supported by a family of hemi-salen type ligands bearing hemilabile thiophenyl (2a), furfuryl (2b) and pyridyl (2c) pendant donor arms. Shelf-life and stability of these complexes followed the trend 2a < 2b < 2c, showing direct correlation to the affinity of the pendant donor group to the indium center. Reactivity towards polymerization of epichlorohydrin and cyclohexene oxide followed the trend 2a > 2b > 2c with control of polymerization following an inverse relationship to reactivity. Surprisingly, 2c polymerized racemic lactide without an external initiator, likely through an alkyl-initiated coordination-insertion mechanism.