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.

A series of amido Ca and Yb(II) complexes LM[N(SiMe)](THF) (1Yb, 1-4Ca) coordinated by amidine-amidopyridinate ligands L were synthesized via a transamination reaction between proligands LH and bisamido complexes M[N(SiMe)](THF) (M = Yb, Ca). The reactions of Yb[N(SiMe)](THF) with proligands LH-LH containing CF and CHF fragments do not allow for preparing the target Yb(II) complexes, while the Ca analogues were synthesized in good yields. Complexes 1Yb and 1-4Ca were evaluated as precatalysts for hydrophosphination of styrene, p-substituted styrenes, α-Me-styrene, and 2,3-dimethylbutadiene with various primary and secondary phosphines (PhPH, 2,4,6-MeCHPH, 2-CNHPH, PhPH, CyPH). Complexes 1Yb, 1-4Ca performed high catalytic activities in styrene hydrophosphination with PhPH and PhPH and demonstrated high regioselectivity affording exclusively the anti-Markovnikov addition products. For primary PhPH the reactions (1:1 molar ratio of substrates) catalyzed by 1Yb, 1Ca, and 2Ca proved to be highly chemoselective affording the secondary phosphine Ph(PhCHCH)PH; however, complexes 3Ca and 4Ca led to the formation of both secondary and tertiary phosphines in 80:20 and 86:14 ratios. Styrene hydrophosphinations with 2,4,6-MeCHPH and 2-pyridylphosphine for all complexes 1Yb and 1-4Ca proceeded much more slowly compared to PhPH. Addition of 2-CNHPH to styrene catalyzed by complex 1Yb turned out to be non-regioselective and led to the formation of a mixture of Markovnikov and anti-Markovnikov addition products, while all Ca complexes enabled regioselective anti-Markovnikov addition. Complexes 1Ca and 1Yb containing catalytic centers featuring similar ionic radii performed different catalytic activity: the ytterbium analogue proved to be a more active catalyst for intermolecular hydrophosphination of styrene with CyPH, 2-CNHPH, and PhPH, but less active with sterically demanding 2,4,6-MeCHPH. Styrenes containing in p-position electron-donating groups (Me, tBu, OMe) performed with noticeably lower rates in the reactions with PhPH compared to styrene. Complexes 1Yb, 1Ca, 2Ca, 3Ca, and 4Ca enabled addition of PhPH toward the double C═C bond of α-Me-styrene, and the reaction rate for this substrate is noticeably lower; however quantitative conversions were reached in ∼40 h. Complexes 1Ca and 2Ca promoted 1,2-addition of PhPH to 2,3-dimethyl butadiene with excellent regio- and chemoselectivity to afford linear secondary phosphines. Hydrophosphination of inert 1-nonene with PhPH with 40% conversion becomes possible due to the application of complex 2Ca (40 h, 70 °C). The rate law for the hydrophosphination of styrene with PhPH catalyzed by 1Ca was found to agree with the idealized equation: v = k[styrene][1Ca].