The syntheses, characterisation and utilisation of the calcium complexes [{Lx}CaN(SiMe3)2·(THF)] supported by monoanionic, tridentate imino-phosphinanilido chalcogenide ligands {Ph2P(E)-N-C6H4-CHN(Dipp)}- (E = S, {L2}-; E = Se, {L3}-; Dipp = 2,6-diisopropylphenyl) as molecular precatalysts for the heterofunctionalisation of styrene are reported. The protio-ligand {L1}H (for E = O) was obtained upon reaction of the aniline-iminophosphane {Ph2PHN-C6H4-CHN(Dipp)} ({L0}H) and hydrogen peroxide at room temperature. The related sulphide and selenide compounds {L2}H and {L3}H were prepared by treatment of {L0}H with elemental sulphur and selenium. Beside, reaction of {L0}H with Me2S·BH3 yielded the corresponding imino-phosphinanilido borane protio-ligand {Ph2P(BH3)N-C6H4-CHN(Dipp)}H ({L4}H). The heteroleptic calcium complexes [{Lx}CaN(SiMe3)2·(THF)] (E = S, 2; E = Se, 3) were synthesised by one-pot reaction of {L2}H and {L3}H with 2 equiv of [KN(SiMe3)2] and CaI2 at room temperature. The reaction of {L2}H with [KN(SiMe3)2] and CaI2 in 2:2:1 proportions yielded the homoleptic complex [Ca{L2}2] (5). The molecular structures of the protio-ligand {L3}H and complexes 3 and 5 were established by single crystal X-ray analysis. The heteroleptic complexes 2 and 3 constitute moderately efficient precatalysts for the intermolecular hydrophosphination and hydroamination of styrene with diphenylphosphine or pyrrolidine, respectively, to mediate the formation of C-P and C-N σ-bonds. © 2016 The Royal Society of Chemistry.