Indium complexes supported by 1,omega-dithiaalkanediyl-bridged bis(phenolato) ligands: synthesis, structure, and controlled ring-opening polymerization of L-lactide.
Indium bis(phenolato) complexes [In(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(2)SiMe(3), n = 0, 4; L = 1,4-dithiabutanediylbis{4,6-di(2-phenyl-2-propyl)phenolato} (etccp), R = CH(2)SiMe(3), n = 0, 5) were prepared from indium trichloride or from the corresponding tris(alkyl) complexes and 1 equiv of tetradentate 1,omega-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(2)SiMe(3))] (4), and [In(etccp)(CH(2)SiMe(3))] (5). Pseudo-octahedral configuration was found for 2, while square pyramidal structure was observed for 4 and 5. The isopropoxy complexes [In(L)(O(i)Pr)] (L = etbbp, 6; etccp, 7) were synthesized starting with indium tris(isopropoxide). Complex 6 crystallized as homochiral dimer of pseudo-octahedral fragments with bridging mu(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).
Peckermann
Ilja
I
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany.
Kapelski
Andreas
A
Spaniol
Thomas P
TP
Okuda
Jun
J
D000473:Alkanes / Q000737:chemistry*; D002713:Chlorine / Q000737:chemistry; D007204:Indium / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*; D011091:Polyesters / Q000737:chemistry*
D000473:Alkanes; D008024:Ligands; D009942:Organometallic Compounds; D011091:Polyesters; D007204:Indium; C033616:poly(lactide); D002713:Chlorine