Thermally Stable Ln(II) and Ca(II) Bis(benzhydryl) Complexes: Excellent Precatalysts for Intermolecular Hydrophosphination of C-C Multiple Bonds.

A series of Ln(II) and Ca(II) bis(alkyl) complexes with bulky benzhydryl ligands, [( p- tBu-CH)CH]M(L ) (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 MI(THF) ( n = 0-2) and [( p- tBu-CH)CH]Na. In complex 1, the benzhydryl ligands are bound to the metal center in η-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 η-fashion. In complex 2, one ligand is η-coordinated while the second one is η-coordinated to the Sm(II) ion. Complexes 2-4 demonstrated unprecedented thermal stability: no evidence of decomposition was observed after heating their solutions in CD at 100 °C during 72 h. Complex 1 behaves differently: thermolysis in CD 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 PhPH toward the internal C═C bond of Z- and E-stilbenes with 100% conversion under mild conditions. Double sequential hydrophosphination of phenylacetylene with PhPH and PhPH was realized due to the application of Yb(II) complex as a catalyst.