RESUMEN
There is experimental evidence that solid mixtures of the rhodium dimer [Cp*RhCl2]2 and benzo[h] quinoline (BHQ) produce two different polymorphic molecular cocrystals called 4α and 4ß under ball milling conditions. The addition of NaOAc to the mixture leads to the formation of the rhodacycle [Cp*Rh-(BHQ)Cl], where the central Rh atom retains its tetracoordinate character. Isolate 4ß reacts with NaOAc leading to the same rhodacycle while isolate 4α does not under the same conditions. We show that the puzzling difference in reactivity between the two cocrystals can be traced back to fundamental aspects of the intermolecular interactions between the BHQ and [Cp*RhCl2]2 fragments in the crystalline environment. To support this view, we report a number of descriptors of the nature and strength of chemical bonds and intermolecular interactions in the extended solids and in a cluster model. We calculate formal quantum mechanical descriptors based on electronic structure, electron density, and binding and interaction energies including an energy decomposition analysis. Without exception, all descriptors point to 4ß being a transient structure higher in energy than 4α with larger local and global electrophilic and nucleophilic powers, a more favorable spatial and energetic distribution of the frontier orbitals, and a more fragile crystal structure.
RESUMEN
Mechanochemical reactions offer methodological and environmental advantages for chemical synthesis, constantly attracting attention within the scientific community. Besides unmistakable sustainability advantages, the conditions under which mechanochemical reactions occur, namely solventless conditions, sometimes facilitate the isolation of otherwise labile or inaccessible products. Despite these advantages, limited knowledge exists regarding the mechanisms of these reactions and the types of intermediates involved. Nevertheless, in an expanding number of cases, ex situ and in situ monitoring techniques have allowed for the observation, characterization, and isolation of reaction intermediates in mechanochemical transformations. In this Minireview, we present a series of examples in which reactive intermediates have been detected in mechanochemical reactions spanning organic, organometallic, inorganic, and materials chemistry. Many of these intermediates were stabilized by non-covalent interactions, which played a pivotal role in guiding the chemical transformations. We believe that by uncovering and understanding such instances, the growing mechanochemistry community could find novel opportunities in catalysis and discover new mechanochemical reactions while achieving simplification in chemical reaction design.
RESUMEN
The occurrence of crystalline intermediates in mechanochemical reactions might be more widespread than previously assumed. For example, a recent study involving the acetate-assisted C-H activation of N-Heterocycles with [Cp*RhCl2 ]2 by ball milling revealed the formation of transient cocrystals between the reagents prior to the C-H activation step. However, such crystalline intermediates were only observed through stepwise intervallic ex-situ analysis, and their exact role in the C-H activation process remained unclear. In this study, we monitored the formation of discrete, stoichiometric cocrystals between benzo[h]quinoline and [Cp*RhCl2 ]2 by ball milling using in-situ synchrotron X-ray powder diffraction. This continuous analysis revealed an initial cocrystal that transformed into a second crystalline form. Computational studies showed that differences in noncovalent interactions made the [Cp*RhCl2 ]2 unit in the later-appearing cocrystal more reactive towards NaOAc. This demonstrated the advantage of cocrystal formation before the acetate-assisted metalation-deprotonation step, and how the net cooperative action of weak interactions between the reagents in mechanochemical experiments can lead to stable supramolecular assemblies, which can enhance substrate activation under ball-milling conditions. This could explain the superiority of some mechanochemical reactions, such as acetate-assisted C-H activation, compared to their solution-based counterparts.
RESUMEN
This work reports the experimentally studied mechanochemical formation of rhodacycles by ball milling pyridine- and quinoline-derived substrates and [Cp*RhCl2 ]2 in the presence of NaOAc. Ex-situ analysis of the mechanochemical reactions using powder X-ray diffraction (PXRD), solid-state UV-vis spectroscopy and ATR-FTIR spectroscopy revealed the formation of unexpected cocrystals between the substrates and the rhodium dimer prior to the C-H activation step. This sequence of events differs from the generally accepted steps in solution in which cleavage of [Cp*RhCl2 ]2 is initiated by acetate ions. Additionally, the mechanochemical approach enabled the synthesis of the six-membered rhodacycle [Cp*Rh(2-benzilpyridine)Cl], a metal complex repeatedly reported as inaccessible in solution. Altogether, the results of this investigation clarify some of the fundamental aspects of mechanochemical cyclometallations.
RESUMEN
In the search for versatile reagents compatible with mechanochemical techniques, in this work we studied the reactivity of N-fluorobenzenesulfonimide (NFSI) by ball milling. We corroborated that, by mechanochemistry, NFSI can engage in a variety of reactions such as fluorinations, fluorodemethylations, sulfonylations, and amidations. In comparison to the protocols reported in solution, the mechanochemical reactions were accomplished in the absence of solvents, in short reaction times, and in yields comparable to or higher than their solvent-based counterparts.
RESUMEN
In recent years, mechanochemistry has been growing into a widely accepted alternative for chemical synthesis. In addition to their efficiency and practicality, mechanochemical reactions are also recognized for their sustainability. The association between mechanochemistry and Green Chemistry often originates from the solvent-free nature of most mechanochemical protocols, which can reduce waste production. However, mechanochemistry satisfies more than one of the Principles of Green Chemistry. In this Review we will present a series of examples that will clearly illustrate how mechanochemistry can significantly contribute to the fulfillment of Green Chemistry in a more holistic manner.
RESUMEN
Recent progress in the field of mechanochemistry has expanded the discovery of mechanically induced chemical transformations to several areas of science. However, a general fundamental understanding of how mechanochemical reactions by ball milling occur has remained unreached. For this, we have now implemented inâ situ monitoring of a mechanochemically induced molecular rearrangement by synchrotron X-ray powder diffraction, Raman spectroscopy, and real-time temperature sensing. The results of this study demonstrate that molecular rearrangements can be accomplished in the solid state by ball milling and how inâ situ monitoring techniques enable the visualization of changes occurring at the exact instant of a molecular migration. The mechanochemical benzil-benzilic acid rearrangement is the focal point of the study.
RESUMEN
A mechanochemical synthesis of one-dimensional carbon allotrope carbyne model compounds, namely tetraaryl[n]cumulenes (n=3, 5) was realized. Central for the mechanosynthesis of the cumulenic carbon nanostructures were the development of a mechanochemical Favorskii alkynylation-type reaction and the implementation of a solvent-free, acid-free reductive elimination with tin(II) chloride by ball milling.
RESUMEN
In recent times, many biologically relevant building blocks such as amino acids, peptides, saccharides, nucleotides and nucleosides, etc. have been prepared by mechanochemical synthesis. However, mechanosynthesis of lipids by ball milling techniques has remained essentially unexplored. In this work, a multistep synthetic route to access mono- and diacylglycerol derivatives by mechanochemistry has been realized, including the synthesis of diacylglycerol-coumarin conjugates.
RESUMEN
The ability of mechanochemistry to alter established chemical selectivity is demonstrated. A copper(I)-catalyzed mechanochemical aldehyde/alkyne/amine coupling using calcium carbide as the acetylene source provides selective access to 1,4-diamino-2-butynes, which contrasts classical approaches that provide propargylamine-type products. Solventless milling conditions were found to be essential to unmask A3 â coupling products with new compositions.
