Heteroleptic Ln(II) and Ca(II) amides [tBuC(NC6H3-iPr2-2,6)2]MN(SiMe3)2(THF) (M = Yb (1Yb), Ca (1Ca)), [2-MeOC6H4NC(tBu)N(C6H3-iPr2-2,6)]LnN(SiMe3)2(THF) (Ln = Sm (2Sm), Yb (2Yb)), and [2-Ph2P(O)C6H4NC(tBu)N(C6H3-Me2-2,6)]YbN(SiMe3)2(THF) (3Yb) coordinated by bi- and tridentate amidinate ligands were obtained by the amine elimination reactions of M[N(SiMe3)2](THF)2 (M = Yb, Sm, Ca) with parent amidines in good yields. Complex [tBuC(NC6H3-iPr2-2,6)2]SmN(SiMe3)2 can be obtained only by a salt metathesis reaction of [tBuC(NC6H3-2,6-iPr2)2]SmI(THF)2 with NaN(SiMe3)2. Unlike 1Yb and 1Ca in 1Sm the amidinate ligand is coordinated to metal ion in κ(1)-amido:η(6)-arene fashion preventing THF coordination. The derivatives of tridentate amidinate ligands bearing pendant donor 2-MeOC6H4 or 2-Ph2P(O)C6H4N groups feature nonconventional κ(1)-N,κ(2)-O,η(6)-arene coordination mode. Complexes 1Ca, 1Sm, 1Yb, 2Sm, 2Yb, and 3Yb proved to be efficient catalysts for styrene hydrophosphination with PhPH2 and Ph2PH. In styrene hydrophosphination with PhPH2 all the catalysts perform excellent chemoselectivity and afford a monoaddition product-secondary phosphine (PhCH2CH2)PhPH. Moreover, all the catalysts perform hydrophosphination reactions regioselectively with exclusive formation of the anti-Markovnikov addition product. Within the series of complexes coordinated by the same amidinate ligand catalytic activity decreases in the following order 1Ca ≥ 1Sm>1Yb. The turnover frequencies were in the range of TOF ≈ 0.3-0.7 h(-1). However, application of tridentate amidinate ligand allowed one to increase catalytic activity significantly: for 2Sm TOF was found to be 8.3 h(-1). For the addition of PhPH2 to para-substituted styrenes catalyzed by 2Sm it was found that electron-withdrawing substituents (Cl, F) do not affect the reaction rate while electron-donating groups (tBu, OMe) noticeably slow down the reaction.