Rationalizing the formation of porosity in mechanochemically-synthesized polymers.

In this study, we present a matrix of 144 mechanochemically-synthesized polymers. All polymers were constructed by the solvent-free Friedel-Crafts polymerization approach, employing 16 aryl-containing monomers and 9 halide-containing linkers, which were processed in a high-speed ball mill. This Polymer Matrix was utilized to investigate the origin of porosity in Friedel-Crafts polymerizations in detail. By examining the physical state, molecular size, geometry, flexibility, and electronic structure of the utilized monomers and linkers, we identified the most important factors influencing the formation of porous polymers. We analyzed the significance of these factors for both monomers and linkers based on the yield and specific surface area of the generated polymers. Our in-depth evaluation serves as a benchmark study for future targeted design of porous polymers by the facile and sustainable concept of mechanochemistry.

The Sonogashira Coupling on Palladium Milling Balls-A new Reaction Pathway in Mechanochemistry.

Utilizing direct mechanocatalytical conditions, the Sonogashira coupling was successfully performed on the surface of milling tools by using pure Pd and Pd coated steel balls. The optimization of co-catalyst forming additives led to a protocol, which generates quantitative yields under aerobic conditions for various substrates within as little as 90 minutes. Using state-of-the-art spectroscopic, diffractive, as well as in situ methods lead to the identification of a previously unknown and highly reactive complex of the co-catalyst copper. This new complex differs substantially from the known complexes in liquid phase Sonogashira couplings, proving that reaction pathways in mechanochemistry may differ from those in established synthetic procedures.

The impact of the physical state and the reaction phase in the direct mechanocatalytic Suzuki-Miyaura coupling reaction.

The direct mechanocatalytic Suzuki-Miyaura coupling reaction, utilizing palladium milling balls as active catalysts, was investigated regarding the physical state of the reagents and the reaction phase. The substitution patterns and functional groups of different aryl iodides were varied and different boronic acid derivates were utilized to achieve a wide range of substrate combinations. In the neat grinding experiments, liquid aryl iodides were more reactive than solid ones and a steric influence of the substituents, especially pronounced in ortho compounds, was observed. In order to overcome the general low reactivity of the solid phase, several liquid-assisted grinding experiments were conducted and the influence of substrate solubility and catalyst wettability analyzed. Among all LAG additives, EtOH showed the greatest impact on the reactivity, as it converts boronic acid derivatives into liquid and reactive esters under mechanochemical conditions, significantly speeding up the reaction.

The Transformation of Inorganic to Organic Carbonates: Chasing for Reaction Pathways in Mechanochemistry.

Mechanochemical reactions are solvent-free alternatives to solution-based syntheses enabling even conventionally impossible transformations. Their reaction pathways, however, usually remain unexplored within the heavily vibrating, dense milling vessels. Here, we showcase how the green organic solvent diethyl carbonate is synthesized mechanochemically from inorganic alkali carbonates and how the complementary combination of milling parameter studies, synchrotron X-ray diffraction real time monitoring, and quantum chemical calculations reveal the underlying reaction pathways. With this, reaction intermediates are identified, and chemical concepts of solution-chemistry are challenged or corroborated for mechanochemistry.

Mechanochemically-Assisted Synthesis of Polyimides.

Polyimides were obtained in 99 % yield in under 1 h through the "beat and heat" approach, involving solvent-free vibrational ball milling and a thermal treatment step. The influence of a plethora of additives was explored, such as Lewis acids, Lewis bases, and dehydrating agents, and the mechanochemical reaction was identified to run via a polyamic acid intermediate. The protocol was adopted to a range of substrates inaccessible through solution-based processes, including perylene tetracarboxylic acid dianhydride and melamine. Furthermore, quantum chemical calculations were conducted to identify the water removal as the crucial step in the reaction mechanism. The presented method is substantially faster and more versatile than the solution-based process.

Dimerization of Substituted Arylacetylenes-Quantum Chemical Calculations and Kinetic Studies.

The dimerization of substituted arylacetylenes is a very interesting tool to generate 1,3-butadiene 1,4-diradicals. Recently, it was shown that electron-withdrawing groups attached to the triple bond reduce the activation barrier and increase the stability of the diradical intermediates. Here, we investigate the influence of the π donor character of substituents, which are bound to the aryl system, on the dimerization reaction of arylacetylenes. Both quantum chemical calculations and kinetic studies reveal that the higher the π donor character of substituents, the lower the activation barrier. The highest observed difference between the model systems amounts to 4.0 kcal/mol, which represents an acceleration by a factor of 700. However, according to the calculations the π donor character of the substituents increases the diradical character of the intermediates.

Au(I)-Catalyzed Dimerization of Two Alkyne Units-Interplay between Butadienyl and Cyclopropenylmethyl Cation: Model Studies and Trapping Experiments.

In recent years, Au(I)-catalyzed reactions proved to be a valuable tool for the synthesis of substituted cycles by cycloaromatization and cycloisomerization starting from alkynes. Despite the myriad of Au(I)-catalyzed reactions of alkynes, the mono Au(I)-catalyzed pendant to the radical dimerization of nonconjugated alkyne units has not been investigated by quantum chemical calculations. Herein, by means of quantum chemical calculations, we describe the mono Au(I)-catalyzed dimerization of two alkyne units as well as the transannular ring closure reaction of a nonconjugated diyne. We found that depending on the system and the method used either the corresponding cyclopropenylmethyl cation or the butadienyl cation represents the stable intermediate. This circumstance could be explained by different stabilizing effects. Moreover, the calculation reveals a dramatic (>1012-fold) acceleration of the Au(I)-catalyzed reaction compared to that of the noncatalyzed radical variant. Trapping experiments with a substituted 1,6-cyclodecadiyne using benzene as a solvent at room temperature as well as studies with deuterated solvents confirm the calculations. In this context, we also demonstrate that trapping of the cationic intermediate with benzene does not proceed via a Friedel-Crafts-type reaction.

Model studies on the dimerization of 1,3-diacetylenes.

By means of high-level quantum chemical calculations (B2PLYPD and CCSD(T)), the dimerization of 1,3-diacetylenes was studied and compared to the dimerization of acetylene. We found that substituted 1,3-diacetylenes are more reactive than the corresponding substituted acetylenes having an isolated triple bond. The most reactive centers for a dimerization are always the terminal carbon atoms. The introduction of a test reaction allows the calculation of the relative reactivity of individual carbon centers in phenylacetylene, phenylbutadiyne, and phenylhexatriyne. A comparison shows that the reactivity of the terminal carbon atoms increases with increasing numbers of alkyne units, whereas the reactivity of the internal carbon atoms remains very low independent of the number of alkyne units.

Enediyne dimerization vs Bergman cyclization.

High-level quantum chemical calculations reveal that the dimerization of enediynes to 1,3-butadiene-1,4-diyl diradicals is energetically more favored than the corresponding Bergman cyclization of enediynes. Moreover, the activation barrier of both reactions can be drastically reduced by the introduction of electron-withdrawing substituents like fluoro groups at the reacting carbon centers of the triple bonds.

Dimerization of two alkyne units: model studies, intermediate trapping experiments, and kinetic studies.

By means of high level quantum chemical calculations (B2PLYPD and CCSD(T)), the dimerization of alkynes substituted with different groups such as F, Cl, OH, SH, NH2, and CN to the corresponding diradicals and dicarbenes was investigated. We found that in case of monosubstituted alkynes the formation of a bond at the nonsubstituted carbon centers is favored in general. Furthermore, substituents attached to the reacting centers reduce the activation energies and the reaction energies with increasing electronegativity of the substituent (F > OH > NH2, Cl > SH, H, CN). This effect was explained by a stabilizing hyperconjugative interaction between the σ* orbitals of the carbon-substituent bond and the occupied antibonding linear combination of the radical centers. The formation of dicarbenes is only found if strong π donors like NH2 and OH as substituents are attached to the carbene centers. The extension of the model calculations to substituted phenylacetylenes (Ph-C≡C-Y) predicts a similar reactivity of the phenylacetylenes: F > OCH3 > Cl > H. Trapping experiments of the proposed cyclobutadiene intermediates using maleic anhydride as dienophile as well as kinetic studies confirm the calculations. In the case of phenylmethoxyacetylene (Ph-C≡C-OCH3) the good yield of the corresponding cycloaddition product makes this cyclization reaction attractive for a synthetic route to cyclohexadiene derivatives from alkynes.