The coordination chemistry of the aminophosphine chalcogenide ligands [Ph2P(O)NHR], [Ph2P(S)NHR], and [Ph2P(Se)NHR] (R = 2,6-Me2C2H2,tBu, CHPh2, CPh3) or corresponding borane derivative [Ph2P(BH3)NHR] toward group 1 and 2 metals is reviewed. The structural characterization of a huge number of mono- and bis-aminophosphine chalcogenide/borane complexes with group 1 and 2 metals—in most cases lithium, sodium, potassium, magnesium, calcium, strontium, and barium complexes—reveals a poly-metallacyclic motif in each case. The coordination takes place from adjacent chalcogen/borane and nitrogen as donor atom or group of the ligand confirming the direct bond between metal and chalcogen/borane to develop homoleptic and heteroleptic complexes. The heteroleptic group 2 metal complexes were used as precatalysts in hydrophosphination and hydroamination reactions. Similarly, aminophosphine chalcogenide alkaline earth metal complexes were used in the catalytic ring-opening polymerization (ROP) study of ε-caprolactone. © 2017, Taylor and Francis Group, LLC