Herein we present the results of a blind challenge to quantum chemical methods in the calculation of dimerization preferences in the low temperature gas phase. The target of study was the first step of the microsolvation of furan, 2-methylfuran and 2,5-dimethylfuran with methanol. The dimers were investigated through IR spectroscopy of a supersonic jet expansion. From the measured bands, it was possible to identify a persistent hydrogen bonding OH–O motif in the predominant species. From the presence of another band, which can be attributed to an OH-π interaction, we were able to assert that the energy gap between the two types of dimers should be less than or close to 1 kJ/mol across the series. These values served as a first evaluation ruler for the 12 entries featured in the challenge. A tentative stricter evaluation of the challenge results is also carried out, combining theoretical and experimental results in order to define a smaller error bar. The process was carried out in a double-blind fashion, with both theory and experimental groups unaware of the results on the other side, with the exception of the 2,5-dimethylfuran system which was featured in an earlier publication.

The interpretation of chemical properties/phenomena can often be aided through the use of imagery. The mapping of molecular electrostatic potentials is a prime example, serving as a guideline in the design of novel compounds or understanding transition state stabilization effects. It is today a common tool for theoreticians and experimentalists alike. With the emergence of concepts such as dispersion energy donors, and the overall importance of dispersion in chemical systems, representations targeting such a class of interactions are warranted. In this work, we make use of local orbital analysis to extract dispersion interactions and represent them in a scalar quantity, the Dispersion Interaction Density (DID). A particular advantage of the method is the possibility to represent at the same footing intermolecular and intramolecular interactions in a straightforward fashion from wave function calculations. We present examples for the benzene dimer, several substituted benzenes and a coupled diamondoid molecule. © 2016 Wiley Periodicals, Inc.

Despite its cramped interior, a [Pd2L4] coordination cage consisting of bulky adamantyl ligands shows impressive motility and a rich encapsulation chemistry.

C-H/C-C Functionalizations were achieved with the aid of a versatile manganese(I) catalyst. Thus, an organometallic manganese-catalyzed C-H activation set the stage for silver-free C-H/C-C transformations with ample substrate scope and excellent levels of chemo-, site-, and diastereo-selectivities. The robust nature of the manganese(I) catalysis regime was reflected by the first C-H/C-C functionalization on amino acids under racemization-free reaction conditions. Detailed experimental and computational mechanistic studies provided strong evidence for a facile C-H activation and a rate-determining C-C cleavage, with considerable contribution from London dispersion interactions.