Indium Complexes Supported by 1,ω-Dithiaalkanediyl-Bridged Bis(phenolato) Ligands: Synthesis, Structure, and Controlled Ring-Opening Polymerization of L-Lactide

摘要

Indium bis(phenolato) complexes [ln(L)R(THF)_n] (L = 1,4-dithiabutanediylbis(4,6-di-tert-butylphenolato) (etbbp), R = Cl, n = 0, 1; L = 1,3-dithiapropanediylbis(6-tert-butyl-4-methylphenolato) (mtbmp), R = Me, n = 1, 2; L = 1, 4-dithiabutanediyl-bis(6-tert-butyl-4-methyl-phenolato) (etbmp), R = Me, n= 0, 3; L etbbp, R CH_2SiMe_3, n= 0, 4; L = 1,4-dithiabutanediylbis{4,6-di(2-phenyl-2-propyl)phenolato} (etccp), R = CH_2SiMe_3, n = 0, 5) were prepared from indium trichloride or from the corresponding tris(alkyl) complexes and 1 equiv of tetradentate 1,ω-dithiaalkanediyl- bridged bis(phenol) LH_2. The monomeric nature of the alkyl indium complexes was shown by X-ray diffraction studies of the complexes [In(mtbmp)Me(THF)] (2), [In(etbbp)(CH_2SiMe_3)] (4), and [In(etccp)(CH_2SiMe_3)] (5). Pseudo-octahedral configuration was found for 2, while square pyramidal structure was observed for 4 and 5. The isopropoxy complexes [In(L)(0~iPr)] (L etbbp, 6; etccp, 7) were synthesized starting with indium tris(isopropoxide). Complex 6 crystallized as homochiral dimer of pseudo-octahedral fragments with bridging μ_2-alkoxide ligands, but in solution two diastereomers were observed. The isopropoxy complexes efficiently initiated the ring-opening polymerization of L-lactide in toluene to give isotactic poly(L-lactides) with narrow molecular weight distribution (M_w/M_n= 1.03-1.18).