Heteroleptic silylamido phenolate complexes of calcium and the larger alkaline earth metals: β-agostic Ae⋅⋅⋅Si-H stabilization and activity in the ring-opening polymerization of L-lactide.

The factors governing the stability and the reactivity towards cyclic esters of heteroleptic complexes of the large alkaline earth metals (Ae) have been probed. The synthesis and stability of a family of heteroleptic silylamido and alkoxide complexes of calcium [{LO(i)}Ca-Nu(thf)(n)] supported by mono-anionic amino ether phenolate ligands (i = 1, {LO(1)}(-) = 4-(tert-butyl)-2,6-bis(morpholinomethyl)phenolate, Nu(-) = N(SiMe(2)H)(2)(-), n = 0, 4; i = 2, {LO(2)}(-) = 2,4-di-tert-butyl-6-{[2-(methoxymethyl)pyrrolidin-1-yl]methyl}phenolate, Nu(-) = N(SiMe(2)H)(2)(-), n = 0, 5; i = 4, {LO(4)}(-) = 2-{[bis(2-methoxyethyl)amino]methyl}-4,6-di-tert-butylphenolate, Nu(-) = N(SiMe(2)H)(2)(-), n = 1, 6; Nu(-) = HC≡CCH(2)O(-), n = 0, 7) and those of the related [{LO(3)}Ae-N(SiMe(2)H)(2)] ({LO(3)}(-) = 2-[(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)methyl]-4,6-di-tert-butylphenolate Ae = Ca, 1; Sr, 2; Ba, 3) have been investigated. The molecular structures of 1, 2, [(4)(2)], 6, and [(7)(2)] have been determined by X-ray diffraction. These highlight Ae⋅⋅⋅H-Si internal β-agostic interactions, which play a key role in the stabilization of [{LO(i)}Ae-N(SiMe(2)H)(2)] complexes against ligand redistribution reactions, in contrast to regular [{LO(i)}Ae-N(SiMe(3))(2)]. Pulse-gradient spin-echo (PGSE) NMR measurements showed that 1, 4, 6, and 7 are monomeric in solution. Complexes 1-7 mediate the ring-opening polymerization (ROP) of L-lactide highly efficiently, converting up to 5000 equivalents of monomer at 25 °C in a controlled fashion. In the immortal ROP performed with up to 100 equivalents of exogenous 9-anthracenylmethanol or benzyl or propargyl alcohols as a transfer agent, the activity of the catalyst increased with the size of the metal (1<2<3). For Ca-based complexes, the enhanced electron-donating ability of the ancillary ligand favored catalyst activity (1>6>4≈5). The nature of the alcohol had little effect over the activity of the binary catalyst system 1/ROH; in all cases, both the control and end-group fidelity were excellent. In the living ROP of L-LA, the HC≡CCH(2)O(-) initiating group (as in 7) proved superior to N(SiMe(2)H)(2)(-) or N(SiMe(3))(2)(-) (as in 6 or [{LO(4)}Ca-N(SiMe(3))(2)] (B), respectively).