Search results for "Pseudorotation"
showing 6 items of 6 documents
Orbiting Orbitals: Visualization of Vi-Bronic Motion at a Conical Intersection
2013
The Jahn-Teller (JT) active unpaired electron of single metalloporphyrin radical anions is imaged through scanning tunneling microscopy. It is demonstrated that the electron is delocalized over the porphyrin macrocycle and its topographic image is determined by vibronic motion: the orbital of the electron adiabatically follows the zero-point pseudorotation of skeletal deformations. Transformation of the polar graphs of the observed images allows visualization of the adiabatic vibrational density to which the electron is coupled. The vibronic potential at the conical intersection is visualized and the half-integer angular momentum characteristic of the Berry phase is revealed in the radial f…
Pyrrolidine in Drug Discovery: A Versatile Scaffold for Novel Biologically Active Compounds
2021
AbstractThe five-membered pyrrolidine ring is one of the nitrogen heterocycles used widely by medicinal chemists to obtain compounds for the treatment of human diseases. The great interest in this saturated scaffold is enhanced by (1) the possibility to efficiently explore the pharmacophore space due to sp3-hybridization, (2) the contribution to the stereochemistry of the molecule, (3) and the increased three-dimensional (3D) coverage due to the non-planarity of the ring—a phenomenon called “pseudorotation”. In this review, we report bioactive molecules with target selectivity characterized by the pyrrolidine ring and its derivatives, including pyrrolizines, pyrrolidine-2-one, pyrrolidine-2…
Darstellung einiger oligomerer Cyclo{oligo[(2-hydroxy-1,3-phenylen)methylen]}e. Spektroskopische Untersuchung ihrer Pseudorotation
1978
Es wird die Darstellung von Cyclo{tris[(2-hydroxy-5-methyl-1,3-phenylen)methylen]-(2-hydroxy-5-tert-butyl-1,3-phenylen)methylen} (4a), Cyclo{bis[(2-hydroxy-5-methyl-1,3-phenylen)methylen]-bis[(2-hydroxy-5-tert-butyl-1,3-phenylen)methylen]}(4b) und Cyclo-{pentakis[(2-hydroxy-5-methyl-1,3-phenylen)methylen]} (4c) beschrieben. Die IR-Spektren zeigen, das die phenolischen Hydroxygruppen der Vierringverbindungen 4a und 4b intramolekulare, vom Losungs(CCl4)- oder Zerteilungsmittel (KBr) weitgehend unabhangige Wasserstoffbrucken bilden, die bei der pentameren Ringverbindung 4c schwacher sind. Anhand der 1H-NMR-Spektren last sich bei diesen Verbindungen eine Pseudorotation nachweisen. Die Massenspe…
Stufenweise darstellung eines cycloheptamers aus p-kresol, 4-tert-butylphenol und formaldehyd. Vergleich mit einem phenolischen, heptanuklearen kette…
1980
A phenolic cycloheptamer (11) and an analogous chain oligomer (10) with nearly the same structure were gained by stepwise syntheses. The cycloheptamer has a higher melting point and a better solubility in chloroform. In contrast to the chain oligomer his infrared spectrum indicates a stronger association of the hydroxyl groups which is not influenced by the solvent. The mass spectra announce a preferred statistical cleavage along the chain of compound 10 and a great stability of the ring of 11 which preferentially loses his substituents. The 1H NMR spectra confirm the constitutions of the chain (10) and ring compound (11). The cycloheptamer is distinguished by a ring inversion or a pseudoro…
Schrittweise synthesen und eigenschaften einiger cyclopentamerer aus methylenverbrückten (5-alkyl-2-hydroxy-1,3-phenylen)-bausteinen
1981
Three cyclopentamers (2a–c) and a chainlike pentanuclear oligomer (3a) were prepared by stepwise syntheses. The molecules of the cyclic compounds with 20 links contain o,o′-methylene bridged 2-hydroxy-5-methyl-1,3-phenylene or 2-hydroxy-5-tert-butyl-1,3-phenylene units in a strictly defined manner. The properties of the cyclic pentamer 2a and the chainlike pentanuclear oligomer 3a were compared. They differ by their solubilities, melting points, IR and 1H NMR spectra (pseudorotation) and fragmentation behaviour shown by their mass spectra. The pseudorotation of the cyclic compounds were quantitatively studied.
On the mechanism of imine elimination from Fischer tungsten carbene complexes
2016
(Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)tungsten(0) (CO)5W=C(NHFc)Fc (W(CO)5(E-2)) is synthesized by nucleophilic substitution of the ethoxy group of (CO)5W=C(OEt)Fc (M(CO)5(1Et)) by ferrocenyl amide Fc-NH– (Fc = ferrocenyl). W(CO)5(E-2) thermally and photochemically eliminates bulky E-1,2-diferrocenylimine (E-3) via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E-3 are performed by NMR, IR and UV–vis spectroscopy and liquid injection field desorption ionization (LIFDI) mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO)5(E-2) decays thermally i…