{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T21:44:58Z","timestamp":1791323098273,"version":"4.3.1"},"reference-count":106,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2005,10,14]],"date-time":"2005-10-14T00:00:00Z","timestamp":1129248000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2006,1]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A series of new alkoxy\u2010amino\u2010bis(phenols) (H<jats:sub>2<\/jats:sub>L <jats:bold>1<\/jats:bold>\u2013<jats:bold>6<\/jats:bold>) has been synthesized by Mannich condensations of substituted phenols, formaldehyde, and amino ethers or diamines. The coordination properties of these dianionic ligands towards yttrium, lanthanum, and neodymium have been studied. The resulting Group 3 metal complexes have been used as initiators for the ring\u2010opening polymerization of <jats:italic>rac<\/jats:italic>\u2010lactide to provide poly(lactic acid)s (PLAs). The polymerizations are living, as evidenced by the narrow polydispersities of the isolated polymers, together with the linear natures of number average molecular weight versus conversion plots and monomer\u2010to\u2010catalyst ratios. Complex [Y(L<jats:bold>6<\/jats:bold>){N(SiHMe<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>}(THF)] (<jats:bold>17<\/jats:bold>) polymerized <jats:italic>rac<\/jats:italic>\u2010lactide to heterotactic PLA (<jats:italic>P<\/jats:italic><jats:sub>r<\/jats:sub> = 0.90 at 20\u2009\u00b0C) and <jats:italic>meso<\/jats:italic>\u2010lactide to syndiotactic PLA (<jats:italic>P<\/jats:italic><jats:sub>r<\/jats:sub> = 0.75 at 20\u2009\u00b0C). The in situ formation of [Y(L<jats:bold>6<\/jats:bold>)(O<jats:italic>i<\/jats:italic>Pr)(THF)] (<jats:bold>18<\/jats:bold>) from <jats:bold>17<\/jats:bold> and 2\u2010propanol resulted in narrower molecular weight distributions (PDI = 1.06). With complex <jats:bold>18<\/jats:bold>, highly heterotactic PLAs with narrow molecular weight distributions were obtained with high activities and productivities at room temperature. The natures of the ligand substituents were shown to have a significant influence on the degree of control of the polymerizations, and in particular on the tacticity of the polymer.<\/jats:p>","DOI":"10.1002\/chem.200500856","type":"journal-article","created":{"date-parts":[[2005,10,14]],"date-time":"2005-10-14T04:47:04Z","timestamp":1129265224000},"page":"169-179","source":"Crossref","is-referenced-by-count":423,"title":["Ring\u2010Opening Polymerization of Lactide with Group 3 Metal Complexes Supported by Dianionic Alkoxy\u2010Amino\u2010Bisphenolate Ligands: Combining High Activity, Productivity, and Selectivity"],"prefix":"10.1002","volume":"12","author":[{"given":"Abderramane","family":"Amgoune","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christophe M.","family":"Thomas","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thierry","family":"Roisnel","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jean\u2010Fran\u00e7ois","family":"Carpentier","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2005,12,9]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-4095(200012)12:23<1841::AID-ADMA1841>3.0.CO;2-E"},{"key":"e_1_2_6_2_2","unstructured":"\u00a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0079-6700(97)00031-2"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200301655"},{"key":"e_1_2_6_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200301655"},{"key":"e_1_2_6_5_2","unstructured":"\u00a0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.19960080406"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3927(20000201)21:3<117::AID-MARC117>3.0.CO;2-X"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1080\/10601329508010289"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0079-6700(01)00039-9"},{"key":"e_1_2_6_10_2","unstructured":"\u00a0"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/b104197p"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr040002s"},{"key":"e_1_2_6_13_2","unstructured":"\u00a0"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/macp.1996.021970902"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3900(200110)175:1<67::AID-MASY67>3.0.CO;2-6"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/cc9960000853"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja002160g"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/b008158m"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic020148e"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja992678o"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja003851f"},{"key":"e_1_2_6_22_2","unstructured":"G. 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J.","year":"1994","journal-title":"Polym. Prepr."},{"key":"e_1_2_6_65_2","first-page":"1155","volume":"196","author":"Stevels W. M.","year":"1995","journal-title":"Macromol. Chem. Phys."},{"key":"e_1_2_6_66_2","first-page":"536","volume":"35","author":"Dubois P.","year":"1994","journal-title":"Polym. Prepr."},{"key":"e_1_2_6_67_2","doi-asserted-by":"publisher","DOI":"10.1002\/pola.10003"},{"key":"e_1_2_6_68_2","unstructured":"For examples of Sn\u2010based alkoxide initiators see:"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma00050a006"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma9509826"},{"key":"e_1_2_6_71_2","first-page":"35","author":"Schwach G.","journal-title":"J. Polym. Sci."},{"key":"e_1_2_6_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma991751s"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/bm020009o"},{"key":"e_1_2_6_74_2","unstructured":"For examples of Al\u2010based alkoxide initiators see:"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma00009a022"},{"key":"e_1_2_6_76_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3927(19991201)20:12<616::AID-MARC616>3.0.CO;2-Z"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja990088k"},{"key":"e_1_2_6_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9930519"},{"key":"e_1_2_6_79_2","unstructured":"For examples of Fe\u2010based alkoxide initiators see:"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma9902753"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja003537l"},{"key":"e_1_2_6_82_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja012689t"},{"key":"e_1_2_6_83_2","unstructured":"For examples of Ln\u2010based alkoxide initiators see:"},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma951813o"},{"key":"e_1_2_6_85_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma9605311"},{"key":"e_1_2_6_86_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma990005k"},{"key":"e_1_2_6_87_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma0000834"},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1039\/b008164g"},{"key":"e_1_2_6_89_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3935(20020401)203:5\/6<889::AID-MACP889>3.0.CO;2-O"},{"key":"e_1_2_6_90_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma970615p"},{"key":"e_1_2_6_91_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma991045r"},{"key":"e_1_2_6_92_2","unstructured":"The high sensitivity of complex18limited its analysis to NMR techniques. Attempts to obtain diffraction\u2010quality single crystals of any of the cumyl\u2010substituted bisphenolate complexes have so far been unsuccessful."},{"key":"e_1_2_6_93_2","unstructured":"Only trace amounts (<5\u2009%) of a second species were observed in this reaction; the unsymmetrical pattern of1H NMR resonances suggests it is a dimer or an aggregated species. Complex18loses its THF ligand upon drying in vacuum to give an unsymmetrical complex as well as indicated by1H NMR spectroscopy in [D6]benzene; see reference [9b]."},{"key":"e_1_2_6_94_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2970001180a"},{"key":"e_1_2_6_95_2","unstructured":"\u00a0"},{"key":"e_1_2_6_96_2","doi-asserted-by":"publisher","DOI":"10.1039\/b000396o"},{"key":"e_1_2_6_97_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0101285"},{"key":"e_1_2_6_98_2","doi-asserted-by":"publisher","DOI":"10.1021\/om010493w"},{"key":"e_1_2_6_99_2","unstructured":"\u00a0"},{"key":"e_1_2_6_100_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39730000126"},{"key":"e_1_2_6_101_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990583p"},{"key":"e_1_2_6_102_2","doi-asserted-by":"publisher","DOI":"10.1039\/a705608g"},{"key":"e_1_2_6_103_2","unstructured":"\u00a0"},{"key":"e_1_2_6_104_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889898007717"},{"key":"e_1_2_6_105_2","unstructured":"G. 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