Preparation of enantiomerically pure open calcocene and strontocene complexes and their application in ring opening polymerizations of rac-lactide.

نویسندگان

  • Ann Christin Fecker
  • Matthias Freytag
  • Peter G Jones
  • Ning Zhao
  • Guofu Zi
  • Marc D Walter
چکیده

The synthesis of C2 symmetric enantiomerically pure open Ca and Sr metallocenes, [(η(5)-pdl*)2Ca(thf)] (1) and [(η(5)-pdl*)2Sr(thf)2] (2) (pdl* = dimethylnopadienyl) is described and these complexes were fully characterized. The solid state structures confirm that the pdl* ligands coordinate exclusively with the less sterically demanding site to the Ca and Sr atoms. These complexes are active catalysts for the controlled ring opening polymerization (ROP) of rac-lactide to give heterotactically enriched polylactides (PL) with narrow polydispersities (PDI = 1.29-1.31) and without adding further activators.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Stereochemistry of lactide polymerization with chiral catalysts: new opportunities for stereocontrol using polymer exchange mechanisms.

The synthesis of chiral aluminum and yttrium alkoxides and their application for lactide polymerization are reported. The complexes (SalBinap)MOR [4, M = Al, R = (i)Pr; 5, M = Y, R = (CH(2))(2)NMe(2)] are synthesized by reacting the ligand (SalBinap)H(2) [2,2'-[(1,1'-binaphthalene)-2,2'-diylbis(nitrilomethylidyne)]bisphenol] with the appropriate metal trisalkoxide. While enantiomerically pure y...

متن کامل

Phosphasalen Indium Complexes Showing High Rates and Isoselectivities in rac‐Lactide Polymerizations

Polylactide (PLA) is the leading bioderived polymer produced commercially by the metal-catalyzed ring-opening polymerization of lactide. Control over tacticity to produce stereoblock PLA, from rac-lactide improves thermal properties but is an outstanding challenge. Here, phosphasalen indium catalysts feature high rates (30±3 m-1  min-1 , THF, 298 K), high control, low loadings (0.2 mol %), and ...

متن کامل

Ring-opening polymerisation of rac-lactide mediated by cationic zinc complexes featuring P-stereogenic bisphosphinimine ligands.

The diastereomerically pure P-stereogenic bis(phosphinimine) ligands 4,6-(ArN[double bond, length as m-dash]PMePh)(2)dbf [Ar = 4-isopropylphenyl (Pipp): rac-4, meso-4; Ar = 2,6-diisopropylphenyl (Dipp): rac-4a; dbf = dibenzofuran] were synthesised and complexed to zinc using a protonation-alkane elimination strategy. The cationic alkylzinc complexes thus obtained, RZn[4,6-(ArN[double bond, leng...

متن کامل

Stereoselective Ring-Opening Polymerization of rac-Lactide with a Single-Site, Racemic Aluminum Alkoxide Catalyst: Synthesis of Stereoblock Poly(lactic acid)

The polymerization of racemic lactide with a racemic aluminum alkoxide catalyst is reported. Microstructural analysis of the polymer produced with H NMR spectroscopy revealed that an isotactic stereoblock poly(lactic acid) formed, where each enantiomerically pure block contained an average of 11 lactide monomer units. The melting point of this polymer, 179 °C, was higher than that of the enanti...

متن کامل

Magnesium complexes containing biphenyl-based tridentate imino-phenolate ligands for ring-opening polymerization of rac-lactide and α-methyltrimethylene carbonate.

A series of racemic 2-[(2'-(dimethylamino)biphenyl-2-ylimino)methyl]-4-R(2)-6-R(1)-phenols (L¹H-L⁴H) were reacted with {Mg[N(SiMe3)2]2}2 to provide four heteroleptic magnesium complexes (L¹⁻⁴)MgN(SiMe3)2·(THF)n (1, R(1) = (t)Bu, R(2) = Me, n = 1; 2, R(1) = R(2) = CMe2Ph, n = 0; 3, R(1) = CPh3, R(2) = (t)Bu, n = 1; 4, R(1) = Br, R(2) = (t)Bu, n = 0), which have been fully characterized. X-ray st...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Dalton transactions

دوره 44 37  شماره 

صفحات  -

تاریخ انتشار 2015