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

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Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland, and
Institute für Organische Chemie und Biochemie, Albert-Ludwigs-Unversität, Freiburg, Germany
Cite this: J. Phys. Chem. B 2012, 116, 49, 14406–14415
Publication Date (Web):November 5, 2012
Copyright © 2012 American Chemical Society

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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.

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    Additional calculated IR spectra, and calculated and experimentally measured NMR spectra, together with tables and plots concerning the force field parameters and potential energy surface of cis-[Cl2Pt(6-DPPon)2] complex, are provided. This material is available free of charge via the Internet at

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