Group 3 metal complexes supported by tridentate pyridine- and thiophene-linked bis(naphtholate) ligands: synthesis, structure, and use in stereoselective ring-opening polymerization of racemic lactide and beta-butyrolactone

Dalton Transactions : an International Journal of Inorganic Chemistry
Ekaterina GrunovaJean-François Carpentier

Abstract

Scandium, yttrium and lanthanum amido complexes supported by tridentate bis(ortho-silyl-substituted naphtholate)-donor ligands ({ONO(SiPh3)}(2-) and {ONO(SitBuMe2)}(2-), donor = 2,6-pyridine; {OSO(SiPh3)}(2-), donor = 2,5-thiophene) have been prepared in high yields (72-96%) by reaction of the corresponding pro-ligand {OZO(SiR3)}H(2) and Ln[N(SiHMe(2))(2)](3)(THF)(n) precursor. The solid-state structures of {ONO(SiPh3)}La[N(SiHMe(2))(2)](THF) (3), {ONO(SitBuMe2)}Ln[N(SiHMe(2))(2)](THF) (Ln = Sc, 4; Y, 5) and {OSO(SiPh3)}Ln[N(SiHMe(2))(2)](THF) (Ln = Sc, 7; La, 9) have been determined by single-crystal X-ray diffraction studies. In all five complexes, the naphtholate rings twist in the same direction from the plane of the pyridine or thiophene linker, to give rise to C(s)-symmetric (non crystallographic) structures. Compounds are 1-9 single-site initiators for the ring-opening polymerization (ROP) of racemic lactide (rac-LA) at 20 degrees C, affording poly(lactides)s (PLAs) with relatively narrow polydispersities and molecular weights in good agreement with calculated values. When carried out in THF, the polymerizations afforded heterotactic-enriched PLAs (P(r) up to 0.93), while atactic polymers are formed in toluene. Compounds...Continue Reading

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Citations

Aug 13, 2011·Chemical Communications : Chem Comm·Emma L WhitelawMatthew D Jones
Oct 21, 2011·Chemical Communications : Chem Comm·Ben J JefferyMatthew D Jones
Jun 3, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Yulia ChapurinaJean-François Carpentier
Jul 17, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Wei-Li KongZhong-Xia Wang
Sep 21, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Emma L WhitelawMatthew D Jones
May 7, 2011·Journal of the American Chemical Society·Yann SarazinJean-François Carpentier
Apr 30, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Kuo-Fu PengChi-Tien Chen
May 11, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Peng WangXia Chen
Nov 1, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Bor-Hunn HuangBao-Tsan Ko
Jul 22, 2014·Angewandte Chemie·Clare BakewellCharlotte K Williams
Oct 17, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Nichabhat DiteepengDermot O'Hare
Jun 9, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Abdullah Fahad A AlshamraniCarl Redshaw

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