Hydrogen-Bond and Solvent Dynamics in Transition Metal Complexes : a Combined Simulation and NMR-Investigation

Huang, Jing and Haeussinger, Daniel and Gellrich, Urs and Seiche, Wolfgang and Breit, Bernhard and Meuwly, Markus. (2012) Hydrogen-Bond and Solvent Dynamics in Transition Metal Complexes : a Combined Simulation and NMR-Investigation. Journal of Physical Chemistry B, 116 (49). pp. 14406-14415.

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Official URL: http://edoc.unibas.ch/dok/A6083441

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Self-assembling ligands through complementary hydrogen-bonding in the coordination sphere of a transition metal provides catalysts with unique properties for carbon-carbon and carbon-heteroatom formation. Their most distinguishing chemical bonding pattern is a double-hydrogen-bonded motif, which determines much of the chemical functionality. Here, we discuss the possibility of double proton transfer (DPT) along this motif using computational and experimental methods. The infrared and NMR spectral signatures for the double-hydrogen-bonded motif are analyzed. Atomistic simulations and experiments suggest that the dynamics of the catalyst is surprisingly complex and displays at least three different dynamical regimes which can be distinguished with NMR spectroscopy and analyzed from computation. The two hydrogen bonds are kept intact and in rapid tautomeric exchange down to 125 K, which provides an estimate of 5 kcal/mol for the barrier for DPT. This is confirmed by the simulations which predict 5.8 kcal/mol for double proton transfer. A mechanistic interpretation is provided and the distribution of the solvent shell surrounding the catalyst is characterized from extensive simulations.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Nuclear Magnetic Resonance (Häussinger)
UniBasel Contributors:Meuwly, Markus and Huang, Jing and Häussinger, Daniel
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:02 Mar 2018 11:12
Deposited On:24 May 2013 09:02

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