Nucleophilic Aromatic Substitution at Benzene with Powerful Strontium Hydride and Alkyl Complexes.

Key to the isolation of the first alkyl strontium complex was the synthesis of a strontium hydride complex that is stable towards ligand exchange reactions. This goal was achieved by using the super bulky β-diketiminate ligand DIPeP BDI (CH[C(Me)N-DIPeP]2 , DIPeP=2,6-diisopentylphenyl). Reaction of DIPeP BDI-H with Sr[N(SiMe3 )2 ]2 gave (DIPeP BDI)SrN(SiMe3 )2 , which was converted with PhSiH3 into [(DIPeP BDI)SrH]2 . Dissolved in C6 D6 , the strontium hydride complex is stable up to 70 °C. At 60 °C, H-D isotope exchange gave full conversion into [(DIPeP BDI)SrD]2 and C6 D5 H. Since H-D exchange with D2 is facile, the strontium hydride complex served as a catalyst for the deuteration of C6 H6 by D2 . Reaction of [(DIPeP BDI)SrH]2 with ethylene gave [(DIPeP BDI)SrEt]2 . The high reactivity of this alkyl strontium complex is demonstrated by facile ethylene polymerization and nucleophilic aromatic substitution with C6 D6 , giving alkylated aromatic products and [(DIPeP BDI)SrD]2 .