A series of Ln(II) and Ca(II) bis(alkyl) complexes with bulky benzhydryl ligands, [( p- tBu-C₆H₄)₂CH]₂M(L _n) (M = Sm, L = DME, n = 2 (1); M = Sm, Yb, Ca, L = TMEDA, n = 1 (2, 3, 4), were synthesized by the salt-metathesis reaction of MI₂(THF) _n ( n = 0-2) and [( p- tBu-C₆H₄)₂CH]^-Na⁺. In complex 1, the benzhydryl ligands are bound to the metal center in η²-coordination mode. Unlike complex 1, in isomorphous complexes 3 and 4, due to the coordination unsaturation of the metal center, the both benzhydryl ligands coordinate to the metal in η³-fashion. In complex 2, one ligand is η³-coordinated while the second one is η⁴-coordinated to the Sm(II) ion. Complexes 2-4 demonstrated unprecedented thermal stability: no evidence of decomposition was observed after heating their solutions in C₆D₆ at 100 °C during 72 h. Complex 1 behaves differently: thermolysis in C₆D₆ solution at 75 °C results in total decomposition in 8 h. Addition of DME promotes decomposition of 2-4 and makes it feasible at 40 °C. Complexes 1-4 demonstrated high catalytic activity and excellent regio- and chemoselectivities in intermolecular hydrophosphination of double and triple C-C bonds with both primary and secondary phosphines. Complexes 2 and 3 enable addition of PhPH₂ toward the internal C═C bond of Z- and E-stilbenes with 100% conversion under mild conditions. Double sequential hydrophosphination of phenylacetylene with Ph₂PH and PhPH₂ was realized due to the application of Yb(II) complex as a catalyst.

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