Lithium Complexes Derived of Benzylphosphines: Synthesis, Characterization and Evaluation in the ROP of rac-Lactide and ?-Caprolactone.

ABSTRACT: A series of lithium complexes ([Ph?P(o-C?H?-CH?Li·TMEDA)] (1-Li), [PhP(o-C?H?-CH?)(o-C?H?-CH?Li·TMEDA)] (2-Li), [PhP(o-C?H?-CH?Li·TMEDA)?] (2-Li?) and [P(o-C?H?-CH?Li·TMEDA)?] (3-Li?)) was prepared from mono-, di- and tri-benzylphosphines and varying amounts of nBuLi and was characterized extensively by IR and ¹H, ?Li, 13C and 31P NMR spectroscopy. The molecular structures of complexes 1-Li and 2-Li were determined by single-crystal X-ray diffraction studies. The two complexes have monomeric structures in the solid state comprising seesaw lithium atoms. In each case, the ligand exhibits an asymmetric C-C ?²-coordination mode and an intramolecular P-Li bond interaction. Theoretical calculations at Density functional theory (DFT) level M06/6111+G(2d,p) show that indeed a P-Li bond is established which can be explained as the P lone pair (sp1.26) being partially delocalized on an available sp² orbital on Li (sp2.04) and additional bonding contribution of the phosphorous atom to Li stems from further delocalization of a ? P-C orbital into the sp² orbital on Li. The observed short contact distances between an aromatic ipso carbon and Li in the crystal structures of 1-Li and 2-Li are explained as due to the interaction of a ? C-Li orbital into the ?* orbital of a C-C aromatic bond. Preliminary tests show compounds 1-Li, 2-Li, 2-Li? and 3-Li? are active catalysts in the solvent free ring-opening polymerization (ROP) of ?-caprolactone (?-CL) and rac-lactide (rac-LA). High conversions to polycaprolactones were obtained in short periods of time: 1-6 min at 25 °C. Additionally, all four lithium complexes behave as moderately good initiators for the ROP of rac-LA showing high conversions to polylactides at 140 °C in one hour.

SUBMITTER: Rufino-Felipe E 

PROVIDER: S-EPMC6017396 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature