A series of amido Ca and Yb(II) complexes LM[N(SiMe₃)₂](THF) (1Yb, 1-4Ca) coordinated by amidine-amidopyridinate ligands L^1-4 were synthesized via a transamination reaction between proligands L^1-4H and bisamido complexes M[N(SiMe₃)₂]₂(THF)₂ (M = Yb, Ca). The reactions of Yb[N(SiMe₃)₂]₂(THF)₂ with proligands L²H-L⁴H containing CF₃ and C₆H₄F 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 (PhPH₂, 2,4,6-Me₃C₆H₂PH₂, 2-C₅NH₄PH₂, Ph₂PH, Cy₂PH). Complexes 1Yb, 1-4Ca performed high catalytic activities in styrene hydrophosphination with PhPH₂ and Ph₂PH and demonstrated high regioselectivity affording exclusively the anti-Markovnikov addition products. For primary PhPH₂ the reactions (1:1 molar ratio of substrates) catalyzed by 1Yb, 1Ca, and 2Ca proved to be highly chemoselective affording the secondary phosphine Ph(PhCH₂CH₂)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-Me₃C₆H₂PH₂ and 2-pyridylphosphine for all complexes 1Yb and 1-4Ca proceeded much more slowly compared to PhPH₂. Addition of 2-C₅NH₄PH₂ 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 Cy₂PH, 2-C₅NH₄PH₂, and PhPH₂, but less active with sterically demanding 2,4,6-Me₃C₆H₂PH₂. Styrenes containing in p-position electron-donating groups (Me, tBu, OMe) performed with noticeably lower rates in the reactions with PhPH₂ compared to styrene. Complexes 1Yb, 1Ca, 2Ca, 3Ca, and 4Ca enabled addition of PhPH₂ 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 PhPH₂ to 2,3-dimethyl butadiene with excellent regio- and chemoselectivity to afford linear secondary phosphines. Hydrophosphination of inert 1-nonene with Ph₂PH 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 Ph₂PH catalyzed by 1Ca was found to agree with the idealized equation: v = k[styrene]¹[1Ca]¹.

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