The past decade has witnessed some remarkable advances in our appreciation of the structural and reaction chemistry of the heavier alkaline earth (Ae = Mg, Ca, Sr, Ba) elements.

Despite the routine employment of Grignard reagents and Hauser bases as stoichiometric carbanion reagents in organic and inorganic synthesis, a defined reaction chemistry encompassing the heavier elements of Group II (M = Ca, Sr and Ba) has, until recently, remained unreported. This article provides details of the recent progress in heavier Group II catalysed small molecule transformations mediated by well-defined heteroleptic and homoleptic complexes of the form LMX or MX ₂ ; where L is a mono-anionic ligand and X is a reactive σ-bonded substituent. The intra- and intermolecular heterofunctionalization (hydroamination, hydrophosphination, hydrosilylation and hydrogenation) of alkenes, alkynes, dienes, carbodiimides, isocyanates and ketones is discussed.