Catalysing (organo-)catalysis: Trends in the application of machine learning to enantioselective organocatalysis

• Stefan P. Schmid,
• Leon Schlosser,
• Frank Glorius and
• Kjell Jorner

Beilstein J. Org. Chem. 2024, 20, 2280–2304, doi:10.3762/bjoc.20.196

• dispersion interaction between the DABCOnium system and the CPA is governing the exo-selectivity. For the application of the ML techniques discussed above, it is assumed that all studied reactions follow the same mechanism. If that is not the case, models cannot be reliably fit to the data points, similar to

Complexes of resorcin[4]arene with secondary amines: synthesis, solvent influence on “in-out” structure, and theoretical calculations of non-covalent interactions

• Waldemar Iwanek

Beilstein J. Org. Chem. 2023, 19, 1525–1536, doi:10.3762/bjoc.19.109

• of non-covalent interactions within various types of supramolecular complexes [17]. One such method is HFLD [18], which can be considered a dispersion-corrected HF approach where the dispersion interaction between fragments is added at the DLPNO-CC level. The HFLD method demonstrates comparable

A new oxidatively stable ligand for the chiral functionalization of amino acids in Ni(II)–Schiff base complexes

• Alena V. Dmitrieva,
• Oleg A. Levitskiy,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2023, 19, 566–574, doi:10.3762/bjoc.19.41

• isomer (see Figure 2). The presence of the tert-butyl group induces an additional dispersion interaction between this group and the benzyl fragment in the ʟ-(AlaNi)L7 complex, bringing the benzyl group and the o-phenylene moiety even closer to each other (the distance between the C20 and C8 atoms is 3.45

Anion-driven encapsulation of cationic guests inside pyridine[4]arene dimers

• Anniina Kiesilä,
• Jani O. Moilanen,
• Anneli Kruve,
• Christoph A. Schalley,
• Perdita Barran and
• Elina Kalenius

Beilstein J. Org. Chem. 2019, 15, 2486–2492, doi:10.3762/bjoc.15.241

• different geometries, [12 + Me4Nexo1]+ and [12 + Me4Nexo2]+ (Figure S7, Supporting Information File 1). In [12 + Me4Nexo1]+, the Me4N+ cation interacts with the lower rim isobutyl groups only when the dispersion interaction is included in calculations, whereas at the PBE0/def2-TZVP level [12 + Me4Nexo1]+ is

• + 2Iexo]−, increases from −152 kJ/mol to −342 kJ/mol, and −521 kJ/mol, respectively, when the amount of I− anions is increased in the complex. Moreover, the calculated interaction energies illustrate well that the dispersion interaction has considerable influence on the interaction energies of [12

• already sufficiently large supramolecular systems in which the omnipresent dispersion interaction can add up to a substantial force due to multiple interaction sites. Calculations were also carried out for 2, 22, [22 + Me4Nendo]+, [22 + Iexo]−, and [22 + 2Iexo]2−, at the PBE0-D3/def2-TZVP level of theory

Adhesion, forces and the stability of interfaces

• Robin Guttmann,
• Johannes Hoja,
• Christoph Lechner,
• Reinhard J. Maurer and
• Alexander F. Sax

Beilstein J. Org. Chem. 2019, 15, 106–129, doi:10.3762/bjoc.15.12

• for bulk properties of liquids and molecular crystals. The dispersion interaction is one of the four basic interactions types – electrostatics, induction, dispersion and exchange repulsion – of which all WMIs are composed. The fact that each class of basic interactions covers a wide range explains the

• equivalent. The systems discussed are polyaromatic molecules adsorbed to graphene and carbon nanotubes; dimers of alcohols and amines; cellulose crystals; and alcohols adsorbed onto cellulose surfaces. Keywords: adhesion energy; adhesive force; dispersion interaction; weak molecular interaction

• transfer, although this would mean the creation of a cation–anion pair and, thus, a loss of molecular integrity. What is meant, however, is a polarization of the electron density due to a charge shift, which is covered by the basic induction interactions [2]. Although dispersion interaction is a ubiquitous

Dispersion-mediated steering of organic adsorbates on a precovered silicon surface

• Lisa Pecher,
• Sebastian Schmidt and
• Ralf Tonner

Beilstein J. Org. Chem. 2018, 14, 2715–2721, doi:10.3762/bjoc.14.249

• repulsion is virtually the same for adsorption on the clean (ΔEPauli = 1468 kJ·mol−1) and precovered surface (ΔEPauli = 1467 kJ·mol−1) while small changes in electrostatic (ΔEelstat) and orbital (ΔEorb) contributions compensate each other. This leaves the increase in dispersion interaction by 8 kJ·mol−1 for

Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds – an experimental and theoretical study

• Ana-Maria Preda,
• Małgorzata Krasowska,
• Lydia Wrobel,
• Philipp Kitschke,
• Phil C. Andrews,
• Jonathan G. MacLellan,
• Lutz Mertens,
• Marcus Korb,
• Tobias Rüffer,
• Heinrich Lang,
• Alexander A. Auer and
• Michael Mehring

Beilstein J. Org. Chem. 2018, 14, 2125–2145, doi:10.3762/bjoc.14.187

• that can be plotted either as an isosurface (coral plots) or mapped on an isodensity surface (color gradient) of the electron density. Both plots display the regions with the highest contributions to the dispersion interaction present in the complex. In summary, polymorph 1a is formed by one

• distribution of the dispersion interaction within each dimer. An especially high dispersion energy contribution is observed for dimer 1c-2-1 (−83 kJ mol−1). By looking at the distribution of the dispersion energy (dispersion energy density plots) for this dimer it is noticed that almost the entire monomers

The phenyl vinyl ether–methanol complex: a model system for quantum chemistry benchmarking

• Dominic Bernhard,
• Fabian Dietrich,
• Mariyam Fatima,
• Cristóbal Pérez,
• Hannes C. Gottschalk,
• Axel Wuttke,
• Ricardo A. Mata,
• Martin A. Suhm,
• Melanie Schnell and
• Markus Gerhards

Beilstein J. Org. Chem. 2018, 14, 1642–1654, doi:10.3762/bjoc.14.140

• (frozen-core approximation). Furthermore, we analyzed the relative impact of dispersion interactions in the different complexes through a local orbital analysis of the CCSD (connected) doubles energy terms. The latter discussion is complemented with dispersion interaction density (DID) plots [48]. The

• ) charges as described in [68]. The dispersion interaction energies show an interesting pattern. Although all structures are significantly stabilized by dispersion, with a maximum energy difference of 2.6 kJ/mol when summed all together, the relative weight of the different molecular fragments varies quite

• correspond to the relative, zero-point-corrected energies E0,rel with respect to the OH–O isomer, calculated at the LCCSD(T0)-F12/CBS[T:Q]//B3LYP-D3/def2-TZVP level of theory (cf. Table 1). Dispersion interaction density (DID) plots calculated at the LCCSD/VQZ-F12 level. The brown zones indicate regions of

Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion

• Eric Detmar,
• Valentin Müller,
• Daniel Zell,
• Lutz Ackermann and
• Martin Breugst

Beilstein J. Org. Chem. 2018, 14, 1537–1545, doi:10.3762/bjoc.14.130

• . Based on our investigations, we propose a plausible reaction mechanism for this transformation that is in line with the experimental observations. Additional calculations, including NCIPLOT, dispersion interaction densities, and local energy decomposition analysis, for the model cyanation of 2

• File 1). To further probe the dispersive interaction of the Cp* ligand and the other ligands, we have additionally calculated the dispersion interaction densities (DID) [50] for all intermediates and transition states at the SCS-LMP2/def2-TZVPP level of theory. The DID plots of Figure 4 reveal that

• were subsequently derived from single-point calculations employing the functionals described above, the quadruple-ζ basis set def2-QZVP [52] and the COSMO solvation model [59] for dichloroethane (ε = 10.125). The dispersion interaction densities (DID) [50] were calculated at the SCS-LMP2/def2-TZVPP

Correlation effects and many-body interactions in water clusters

• Andreas Heßelmann

Beilstein J. Org. Chem. 2018, 14, 979–991, doi:10.3762/bjoc.14.83

• dispersion interactions are practically negligible for all studied sytems. The two-body dispersion interaction, however, plays a significant role in the formation of the structures of the water clusters and their stability, since it leads to a distinct compression of the cluster sizes compared to the

• polarisability term of the multipole expansion of the dispersion interaction, which is usually neglected in force fields or dispersion corrected DFT methods, is a quite large positive (for the clusters considered) and anisotropic contribution to the interaction energy of small water clusters [22]. It was found

• theory (SAPT) for the water trimer have revealed that the strongest contribution to the three-body energy originates from the polarisation (induction) energy while the three-body dispersion interaction is rather small [28][29]. Moreover, many-body exchange effects, including exchange–induction and

Local energy decomposition analysis of hydrogen-bonded dimers within a domain-based pair natural orbital coupled cluster study

• Ahmet Altun,
• Frank Neese and
• Giovanni Bistoni

Beilstein J. Org. Chem. 2018, 14, 919–929, doi:10.3762/bjoc.14.79

• different fragments are non-orthogonal in DFT-SAPT. However, both schemes converge to the same asymptotic value. The London dispersion interaction calculated by DFT-SAPT and LED schemes differ by 1 kcal/mol in the equilibrium position, but also converge to the same values in the long range, showing in both

Terahertz spectroscopy of 2,4,6-trinitrotoluene molecular solids from first principles

• Ido Azuri,
• Anna Hirsch,
• Anthony M. Reilly,
• Alexandre Tkatchenko,
• Shai Kendler,
• Oded Hod and
• Leeor Kronik

Beilstein J. Org. Chem. 2018, 14, 381–388, doi:10.3762/bjoc.14.26

• employing them were not always able to achieve satisfactory agreement with experiment, as cautioned in [24]. Recent years have seen major improvements in DFT augmented by pair-wise dispersion interaction terms, to the point where they can be used regularly to predict properties of molecular solids [21][25

• dispersion interaction causes sizable shifts in vibrational frequencies and directly affects the spatial character of the vibrational modes. The agreement between theory and experiment allowed us to distinguish between contributions of the two polymorphs to the observed spectrum. Furthermore, we could show

First principle investigation of the linker length effects on the thermodynamics of divalent pseudorotaxanes

• Andreas J. Achazi,
• Doreen Mollenhauer and
• Beate Paulus

Beilstein J. Org. Chem. 2015, 11, 687–692, doi:10.3762/bjoc.11.78

• linker shows an enhanced binding strength due to electronic effects, namely the dispersion interaction between the linkers from the guest and the host. For the longer linkers this ideal packing is not possible due to steric hindrance. Keywords: density functional theory (DFT); dispersion correction

• first principle calculations show clearly that this enhanced binding is due to electronic effects, namely the dispersion interaction of the two linkers. For the shortest linker this interaction results in a nearly ideal π–π stacking. For the two longer linkers ideal packing is not possible due to steric

Theoretical study of the adsorption of benzene on coinage metals

• Werner Reckien,
• Melanie Eggers and
• Thomas Bredow

Beilstein J. Org. Chem. 2014, 10, 1775–1784, doi:10.3762/bjoc.10.185

• framework that can be substituted with functional groups. The bonding between the surface and the adsorbate is an interplay between electrostatic interaction, including charge transfer (CT) to the surface, and covalent contributions [9][10][11]. In addition, it was found that dispersion interaction plays a

• systems [13]. The D3-dispersion correction to the DFT energy is calculated by summation over pair potentials. Non-additive effects of dispersion interaction can be treated on the basis of three-body terms D3(ABC) [13]. The most recent DFT-D3(BJ) method [16] differs from the original DFT-D3 essentially

• often dominated by dispersion interaction to the aromatic framework. Therefore the study of the bonding between benzene and the metal surfaces is of great interest. In addition, although the adsorption of benzene on some of these surfaces has been subject of previous theoretical studies [29][30][31][32

Substitution effect and effect of axle’s flexibility at (pseudo-)rotaxanes

• Friedrich Malberg,
• Jan Gerit Brandenburg,
• Werner Reckien,
• Oldamur Hollóczki,
• Stefan Grimme and
• Barbara Kirchner

Beilstein J. Org. Chem. 2014, 10, 1299–1307, doi:10.3762/bjoc.10.131

• binding is weakened by approximately 10 kcal/mol, and hydrogen bonds are slightly shortened (by up to 0.2 Å). Keywords: dispersion interaction; hydrogen bond; supramolecular chemistry; template; theoretical chemistry; Introduction Rotaxanes are prototypes for molecular machines and molecular switches [1

• =O stretch mode [27]. Different density functionals, including one functional with an empirical correction for dispersion interaction, for the treatment of such rotaxane complexes were studied. We compared these density functional theory (DFT) results with Møller–Plesset second-order perturbation

• theory (MP2) calculations [29]. The contribution of the London dispersion interaction to the total interaction energy in the gas phase is of the same magnitude as the hydrogen bonding interaction (about −14 kcal/mol). The molecular functionality of rotaxanes is solely based on the interplay of different