Divergent reactivity of [(κ3-L)ThCl2(dme)] with Grignard reagents: Alkylation, ancillary ligand transfer to magnesium, and halide exchange caught in the act

Reaction of [(BDPP)ThCl2(dme)] (1) with 2 equivalents of MeMgBr in OEt2, followed by filtration and layering a toluene solution with hexanes at −30 °C yielded a single large crystal of [{(BDPP)ThX(μ-X)2Mg(OEt2)(μ-Me)}2]·2 toluene (X = Br0.73–0.87/Cl0.13–0.27; 3·2 toluene). This product is the result of halide exchange to form a partially brominated neutral thorium species, which is adducted with MeMgX(OEt2). The complex is then tetrametallic as …