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Unsupported Mg-Alkene Bonding.


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 (Me BDI)Mg+ and (tBu BDI)Mg+ with B(C6 F5 )4 - counterions (Me BDI=CH[C(CH3 )N(DIPP)]2 , tBu BDI=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-(H2 C=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.

SUBMITTER: Thum K 

PROVIDER: S-EPMC7898539 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Unsupported Mg-Alkene Bonding.

Thum Katharina K   Friedrich Alexander A   Pahl Jürgen J   Elsen Holger H   Langer Jens J   Harder Sjoerd S  

Chemistry (Weinheim an der Bergstrasse, Germany) 20201223 7


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 (<sup>Me</sup> BDI)Mg<sup>+</sup> and (<sup>tBu</sup> BDI)Mg<sup>+</sup> with B(C<sub>6</sub> F<sub>5</sub> )<sub>4</sub> <sup>-</sup> counterions (<sup>Me</sup> BDI=CH[C(CH<sub>3</sub> )N(DIPP)]<sub>2</sub> , <sup>tBu</sup> BDI=CH[C(tBu)N(DIPP)]<sub>2</sub> , DIPP=2,6-diisopropylphenyl). Coordination complexes with various mono-  ...[more]

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