Ring‐Shaped Phosphinoamido‐Magnesium‐Hydride Complexes: Syntheses,Structures, Reactivity,and Catalysis

A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L^?=Ph₂PNDip^?, Dip=2,6‐diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand geometry enforces various novel ring and cluster geometries for the heteroleptic compounds. We have studied the stoichiometric reactivity of (LMgH)₄] towards unsaturated substrates, and investigated catalytic hydroborations and hydrosilylations of ketones and pyridines. We found that hydroborations of two ketones with pinacolborane using various Mg precatalysts is very rapid at room temperature with very low catalyst loadings, and ketone hydrosilylation using phenylsilane is rapid at 70 °C. Our studies point to an insertion/σ‐bond metathesis catalytic cycle of an in situ formed “MgH₂” active species.