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Activation of a Metal-Halogen Bond by Halogen Bonding

preprint
submitted on 09.04.2020 and posted on 10.04.2020 by Stefan Huber, Julian Wolf, Florian Huber, Nikita Erochok, Flemming Heinen, Vincent Guerin, Claude Legault, Stefan Kirsch
In recent years, the non-covalent interaction of halogen bonding (XB) has found increasing application in organocatalysis. However, reports of the activation of metal-ligand bonds by XB have so far been limited to a few reactions with elemental iodine or bromine. Herein, we present the activation of metal-halogen bonds by two classes of inert halogen bond donors and the use of the resulting activated complexes in homogenous gold catalysis. The only recently explored class of iodolium derivatives were shown to be effective activators in two test reactions and their activity could be modulated by blocking of the Lewis acidic sites. Bis(benzimidazolium)-based halogen bonding activators provided even more rapid conversion, while the non-iodinated reference compound showed little activity. The role of halogen bonding in the activation of metal-halogen bonds was further investigated by NMR experiments and DFT calculations, which support the mode of activation occurring via halogen bonding.

Funding

ERC Starting Grant #638337

DFG Cluster of Excellence RESOLV, EXC 2033 – 390677874

History

Email Address of Submitting Author

stefan.m.huber@rub.de

Institution

Ruhr-University Bochum

Country

Germany

ORCID For Submitting Author

0000-0002-4125-159X

Declaration of Conflict of Interest

None

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