Jan-Hendrik Lamm

Mechanism of Host–Guest Complex Formation and Identification of Intermediates through NMR Titration and Diffusion NMR Spectroscopy

The formation of host-guest (H-G) complexes between 1,8-bis[(diethylgallanyl)ethynyl]anthracene (H) and the N-heterocycles pyridine and pyrimidine (G) was studied in solution using a combination of NMR titration and diffusion NMR experiments. For the latter, diffusion coefficients of potential host-guest structures in solution were compared with those of tailor-made reference compounds of similar shape (synthesized and characterized by NMR, HRMS, and in part XRD). Highly dynamic behavior was observed in both cases, but with different host-guest species and equilibria. With increasing concentrations of the pyridine guest, the equilibrium H2⇄H2κ(1)-G1⇄HG2 is observed (in the second step a host dimer coordinates one guest molecule); for pyrimidine the equilibrium H2→H1κ(2)-G1⇄HG2 is observed (the formation of a 1:1 aggregate is the second step).

Regiochemical Control in Triptycene Formation-An Exercise in Subtle Balancing Multiple Factors

Abstract Reactions between 1,8‐dichloroanthracenes with substituents in position 10 and ortho‐chloroaryne afford mixtures of 1,8,13‐ (syn) and 1,8,16‐trichlorotriptycenes (anti). The syn/anti ratio is dependent on these substituents. Electropositive substituents like SiMe3 and GeMe3 lead to preferred formation of the syn‐isomer, whereas CMe3 groups exclusively afford the anti‐isomer. Different quantum chemical calculations including location of transition states give conflicting results, but indicate the importance of dispersion forces for an at least qualitative prediction of results. The syn‐trichlorotriptycenes with SiMe3 and GeMe3 substituents were characterized by using NMR spectroscopy, mass spectrometry, and X‐ray diffraction experiments.

Bi- and tridentate silicon-based acceptor molecules

Abstract Triethynylphenylsilane (1), trivinylphenylsilane (2), diethynyldiphenylsilane (3) and diphenyldivinylsilane (4) were reacted with chlorodimethylsilane yielding the corresponding hydrosilylation products. To increase their Lewis acidity, the Si–Cl functions were directly transferred into Si–C6F5 units by salt elimination reactions leading to the (semi-) flexible molecules 5–8 bearing two or three Lewis-acidic sidearms. With the aim of providing host-guest complexes, the air-stable and readily soluble compounds 5–8 were converted with N- and O-Lewis bases of different size and geometry. In all cases, NMR spectroscopic investigations reveal no formation of Lewis acid-base complexes. X-ray diffraction experiments of host compounds 5–7 show intermolecular aryl…perfluoroaryl interactions of dispersion nature in the solid state. By hydrosilylation of 1 with trichlorosilane the more Lewis-acidic all-trans-tris[(trichlorosilyl)vinyl]phenylsilane (9) was obtained. Its Lewis acidity was further increased by fluorination to yield all-trans-tris[(trifluorosilyl)vinyl]phenylsilane (10); the conversion with nitrogen containing Lewis bases ends up in the formation of insoluble precipitates.