Unsupported Mg-Alkene Bonding.

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 ( BDI)Mg and ( BDI)Mg with B(C F ) counterions ( BDI=CH[C(CH )N(DIPP)] , BDI=CH[C(tBu)N(DIPP)] , 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-(H C=CEt ) 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 Mg ion-induced dipole interactions.