Transition metal complexes with cage-opened diamondoid tetracyclo[7.3.1.1<sup>4,12</sup>.0<sup>2,7</sup>]tetradeca-6.11-diene

Valentin, Lars; Henß, Anja; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Becker, Jonathan; Würtele, Christian; Schindler, Siegfried

doi:10.1080/00958972.2015.1071802

Cited by 1 publication

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“…In the condensed phase, diamondoid derivatives with open‐cage structures have been prepared by chemical reactions [21] . Such species are of interest, because they are well suited for complexation with transition metals [22] . Studying the opening process of diamondoid cages is also of interest for understanding chemical reactions in which cage opening and reclosing occurs.…”

Section: Introductionmentioning

confidence: 99%

“…[21] Such species are of interest, because they are well suited for complexation with transition metals. [22] Studying the opening process of diamondoid cages is also of interest for understanding chemical reactions in which cage opening and reclosing occurs. To this end, it has been shown that a reaction of 1-hydroxydiamantane with elemental bromine leads to consecutive opening and reclosing of the cage, providing straightforward access to a class of previously unknown 1,2-disubstituted diamondoid derivatives.…”

Section: Introductionmentioning

confidence: 99%

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Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N₂, and H₂O

George

Dopfer

2022

Chemistry A European J

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Radical cations of diamondoids, a fundamental class of very stable cyclic hydrocarbon molecules, play an important role in their functionalization reactions and the chemistry of the interstellar medium. Herein, we characterize the structure, energy, and intermolecular interaction of clusters of the amantadine radical cation (Ama + , 1-aminoadamantane) with solvent molecules of different interaction strength by infrared photodissociation (IRPD) spectroscopy of massselected Ama + L n clusters, with L=Ar (n � 3) and L=N 2 and H 2 O (n = 1), and dispersion-corrected density functional theory calculations (B3LYPÀ D3/cc-pVTZ). Three isomers of Ama + generated by electron ionization are identified by the vibrational properties of their rather different NH 2 groups. The ligands bind preferentially to the acidic NH 2 protons, and the strength of the NH…L ionic H-bonds are probed by the solvation-induced red-shifts in the NH stretch modes. The three Ama + isomers include the most abundant canonical cage isomer (I) produced by vertical ionization, which is separated by appreciable barriers from two bicyclic distonic iminium ions obtained from cage-opening (primary radical II) and subsequent 1,2 H-shift (tertiary radical III), the latter of which is the global minimum on the Ama + potential energy surface. The effect of solvation on the energetics of the potential energy profile revealed by the calculations is consistent with the observed relative abundance of the three isomers. Comparison to the adamantane cation indicates that substitution of H by the electron-donating NH 2 group substantially lowers the barriers for the isomerization reaction.[a] M.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N₂, and H₂O

George

Dopfer

2022

Chemistry A European J

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Transition metal complexes with cage-opened diamondoid tetracyclo[7.3.1.1^4,12.0^2,7]tetradeca-6.11-diene

Cited by 1 publication

References 39 publications

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N₂, and H₂O

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N₂, and H₂O

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Transition metal complexes with cage-opened diamondoid tetracyclo[7.3.1.14,12.02,7]tetradeca-6.11-diene

Cited by 1 publication

References 39 publications

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N2, and H2O

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N2, and H2O

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Transition metal complexes with cage-opened diamondoid tetracyclo[7.3.1.1^4,12.0^2,7]tetradeca-6.11-diene

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N₂, and H₂O

Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N₂, and H₂O