Unsupported Mg–Alkene Bonding

Language
en
Document Type
Article
Issue Date
2021-02-24
First published
2021-02-01
Issue Year
2021
Authors
Thum, Katharina
Friedrich, Alexander
Pahl, Jürgen
Elsen, Holger
Langer, Jens
Harder, Sjoerd
Editor
Publisher
Wiley‐VCH GmbH
Abstract

Abstract The first intermolecular early main group metal–alkene complexes were isolated. This was enabled by using highly Lewis acidic Mg centers in the Lewis base‐free cations (MeBDI)Mg+ and (tBuBDI)Mg+ with B(C6F5)4− counterions (MeBDI=CH[C(CH3)N(DIPP)]2, tBuBDI=CH[C(tBu)N(DIPP)]2, DIPP=2,6‐diisopropylphenyl). Coordination complexes with various mono‐ and bis‐alkene ligands, typically used in transition metal chemistry, were structurally characterized for 1,3‐divinyltetramethyldisiloxane, 1,5‐cyclooctadiene, cyclooctene, 1,3,5‐cycloheptatriene, 2,3‐dimethylbuta‐1,3‐diene, and 2‐ethyl‐1‐butene. In all cases, asymmetric Mg–alkene bonding with a short and a long Mg−C bond is observed. This asymmetry is most extreme for Mg–(H2C=CEt2) bonding. In bromobenzene solution, the Mg–alkene complexes are either dissociated or in a dissociation equilibrium. A DFT study and AIM analysis showed that the C=C bonds hardly change on coordination and there is very little alkene→Mg electron transfer. The Mg–alkene bonds are mainly electrostatic and should be described as Mg2+ ion‐induced dipole interactions.

Journal Title
Chemistry – A European Journal
Volume
27
Issue
7
Citation
Chemistry - A European Journal 27.7 (2021): S. 2513-2522. <https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202004716>
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