Thermodynamics of complex formation reactions in non-aqueous solvents

Vuuren, C.P.J. Van; Lange, Matthias; Stander, P.P.

doi:10.1016/0040-6031(87)80051-5

Thermochimica Acta

1987

DOI: 10.1016/0040-6031(87)80051-5

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Thermodynamics of complex formation reactions in non-aqueous solvents

C.P.J. Van Vuuren

Matthias Lange

P.P. Stander

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1988

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Reversible Restrain and Release of the Dynamic Valence Isomerization in a Shape‐shifting Bullvalene by Complex Formation

Dohmen,

Paululat,

Ihmels

2024

Chemistry A European J

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In search for structural features that enable the control of the valence isomerization of the fluxional bullvalene, a bullvalene‐bis(harmane) conjugate is identified that acts as chelating ligand in complexes with metal ions. Spectrometric titrations show that this ligand forms 1:1 complexes with Ag+, Cu+, Cu2+, and Zn2+. Importantly, detailed NMR‐spectroscopic analysis at different temperatures reveals that the complexation with Ag+ strongly affects the dynamic isomerization of the bullvalene unit of the ligand such that only one predominant valence isomer is formed, even at 5 °C. Detailed 1H‐NMR‐spectroscopic studies disclose an increased barrier (~11 kJmol–1) of the Cope rearrangement. Furthermore, the addition of hexacyclene displaces the Ag+ from the complex, so that the valence isomerization is accelerated and an equilibrium with two predominant isomers is formed. In turn, repeated addition of Ag+ regains the complex with the restrained isomerization of the bullvalene unit. This method to control the valence isomerism by straightforward chemical stimuli may be used to simplify structural analysis at elevated temperatures, i.e. a feature not available so far with bullvalenes, and it may be employed as functional element in dynamic supramolecular assemblies.

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Reversible Restrain and Release of the Dynamic Valence Isomerization in a Shape‐shifting Bullvalene by Complex Formation

Dohmen,

Paululat,

Ihmels

2024

Chemistry A European J

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The solid state and solution chemistry of dichlorobis(pyridine)cobalt(II)

Jacobs

Vuuren

1989

Transition Met Chem

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