{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T03:07:25Z","timestamp":1791256045391,"version":"4.1.0"},"reference-count":156,"publisher":"Wiley","issue":"10","license":[{"start":{"date-parts":[[2012,1,20]],"date-time":"2012-01-20T00:00:00Z","timestamp":1327017600000},"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":[[2012,3,5]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Several new heteroleptic Sn<jats:sup>II<\/jats:sup> complexes supported by amino\u2010ether phenolate ligands [Sn{LO<jats:sup><jats:italic>n<\/jats:italic><\/jats:sup>}(Nu)] (LO<jats:sup>1<\/jats:sup>=2\u2010[(1,4,7,10\u2010tetraoxa\u201013\u2010azacyclopentadecan\u201013\u2010yl)methyl]\u20104,6\u2010di\u2010<jats:italic>tert<\/jats:italic>\u2010butylphenolate, Nu=NMe<jats:sub>2<\/jats:sub> (<jats:bold>1<\/jats:bold>), N(SiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub> (<jats:bold>3<\/jats:bold>), OSiPh<jats:sub>3<\/jats:sub> (<jats:bold>6<\/jats:bold>); LO<jats:sup>2<\/jats:sup>=2,4\u2010di\u2010<jats:italic>tert<\/jats:italic>\u2010butyl\u20106\u2010(morpholinomethyl)phenolate, Nu=N(SiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub> (<jats:bold>7<\/jats:bold>), OSiPh<jats:sub>3<\/jats:sub> (<jats:bold>8<\/jats:bold>)) and the homoleptic Sn{LO<jats:sup>1<\/jats:sup>}<jats:sub>2<\/jats:sub> (<jats:bold>2<\/jats:bold>) have been synthesized. The alkoxy derivatives [Sn{LO<jats:sup>1<\/jats:sup>}(OR)] (OR=O<jats:italic>i<\/jats:italic>Pr (<jats:bold>4<\/jats:bold>), (<jats:italic>S<\/jats:italic>)\u2010OCH(CH<jats:sub>3<\/jats:sub>)CO<jats:sub>2<\/jats:sub><jats:italic>i<\/jats:italic>Pr (<jats:bold>5<\/jats:bold>)), which were generated by alcoholysis of the parent amido precursor, were stable in solution but could not be isolated. [Sn{LO<jats:sup>1<\/jats:sup>}]<jats:sup>+<\/jats:sup>[H<jats:sub>2<\/jats:sub>N{B(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>}<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> (<jats:bold>9<\/jats:bold>), a rare well\u2010defined, solvent\u2010free tin cation, was prepared in high yield. The X\u2010ray crystal structures of compounds <jats:bold>3<\/jats:bold>, <jats:bold>6<\/jats:bold>, and <jats:bold>8<\/jats:bold> were elucidated, and compounds <jats:bold>3<\/jats:bold>, <jats:bold>6<\/jats:bold>, <jats:bold>8<\/jats:bold>, and <jats:bold>9<\/jats:bold> were further characterized by <jats:sup>119<\/jats:sup>Sn M\u00f6ssbauer spectroscopy. In the presence of <jats:italic>i<\/jats:italic>PrOH, compounds <jats:bold>1<\/jats:bold>\u2013<jats:bold>5<\/jats:bold>, <jats:bold>7<\/jats:bold>, and <jats:bold>9<\/jats:bold> catalyzed the well\u2010controlled, immortal ring\u2010opening polymerization (<jats:italic>i<\/jats:italic>ROP) of <jats:sc>L<\/jats:sc>\u2010lactide (<jats:sc>L<\/jats:sc>\u2010LA) with high activities (ca. 150\u2013550\u2005mol<jats:sub>L\u2212LA<\/jats:sub>\u2009mol<jats:sub>Sn<\/jats:sub><jats:sup>\u22121<\/jats:sup>\u2005h<jats:sup>\u22121<\/jats:sup>) for tin(II) complexes. The cationic compound <jats:bold>9<\/jats:bold> required a higher temperature (100\u2009\u00b0C) than the neutral species (60\u2009\u00b0C); monodisperse poly(<jats:sc>L<\/jats:sc>\u2010LA)s were obtained in all cases. The activities of the heteroleptic pre\u2010catalysts <jats:bold>1<\/jats:bold>, <jats:bold>3<\/jats:bold>, and <jats:bold>7<\/jats:bold> were virtually independent of the nature of the ancillary ligand, and, most strikingly, the homoleptic complex <jats:bold>2<\/jats:bold> was equally competent as a pre\u2010catalyst. Polymerization of trimethylene carbonate (TMC) occurs much more slowly, and not at all in the presence of LA; therefore, the generation of PLA\u2010PTMC copolymers is only possible if TMC is polymerized first. Mechanistic studies based on <jats:sup>1<\/jats:sup>H and <jats:sup>119<\/jats:sup>Sn{<jats:sup>1<\/jats:sup>H}\u2005NMR spectroscopy showed that the addition of an excess of <jats:italic>i<\/jats:italic>PrOH to compound <jats:bold>3<\/jats:bold> yielded a mixture of compound <jats:bold>4<\/jats:bold>, compound [Sn(O<jats:italic>i<\/jats:italic>Pr)<jats:sub>2<\/jats:sub>]<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> <jats:bold>10<\/jats:bold>, and free {LO<jats:sup>1<\/jats:sup>}H in a dynamic temperature\u2010dependent and concentration\u2010dependent equilibrium. Upon further addition of <jats:sc>L<\/jats:sc>\u2010LA, two active species were detected, [Sn{LO<jats:sup>1<\/jats:sup>}(OPLLA)] (<jats:bold>12<\/jats:bold>) and [Sn(OPLLA)<jats:sub>2<\/jats:sub>] (<jats:bold>14<\/jats:bold>), which were also in fast equilibrium. Based on assignment of the <jats:sup>119<\/jats:sup>Sn{<jats:sup>1<\/jats:sup>H}\u2005NMR spectrum, all of the species present in the ROP reaction were identified; starting from either the heteroleptic (<jats:bold>1<\/jats:bold>, <jats:bold>3<\/jats:bold>, <jats:bold>7<\/jats:bold>) or homoleptic (<jats:bold>2<\/jats:bold>) pre\u2010catalysts, both types of pre\u2010catalysts yielded the same active species. The catalytic inactivity of the siloxy derivative <jats:bold>6<\/jats:bold> confirmed that ROP catalysts of the type <jats:bold>1<\/jats:bold>\u2013<jats:bold>5<\/jats:bold> could not operate according to an activated\u2010monomer mechanism. These mechanistic studies removed a number of ambiguities regarding the mechanism of the (<jats:italic>i<\/jats:italic>)ROPs of <jats:sc>L<\/jats:sc>\u2010LA and TMC promoted by industrially relevant homoleptic or heteroleptic Sn<jats:sup>II<\/jats:sup> species.<\/jats:p>","DOI":"10.1002\/chem.201102261","type":"journal-article","created":{"date-parts":[[2012,1,20]],"date-time":"2012-01-20T04:37:53Z","timestamp":1327034273000},"page":"2998-3013","source":"Crossref","is-referenced-by-count":76,"title":["Synthetic and Mechanistic Aspects of the Immortal Ring\u2010Opening Polymerization of Lactide and Trimethylene Carbonate with New Homo\u2010 and Heteroleptic Tin(II)\u2010Phenolate Catalysts"],"prefix":"10.1002","volume":"18","author":[{"given":"Valentin","family":"Poirier","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thierry","family":"Roisnel","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sourisak","family":"Sinbandhit","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Manfred","family":"Bochmann","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jean\u2010Fran\u00e7ois","family":"Carpentier","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yann","family":"Sarazin","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2012,1,20]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr940351u"},{"key":"e_1_2_6_3_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_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/bm034247a"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200301655"},{"key":"e_1_2_6_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200301655"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr040002s"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/marc.201000088"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/B810065A"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","volume-title":"Biopolymers from Renewable Resources","year":"1998"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/B815104K"},{"key":"e_1_2_6_12_2","unstructured":"For reviews on ROP organocatalysts see:"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr068415b"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma9025948"},{"key":"e_1_2_6_15_2","unstructured":"\u00a0"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/b104197p"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2005.07.010"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/b819107g"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/C0PY00204F"},{"key":"e_1_2_6_20_2","unstructured":"For key references on Al initiators 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key references on Group\u2005III and lanthanide initiators see:"},{"key":"e_1_2_6_52_2","first-page":"463","volume":"33","author":"McLain S. J.","year":"1992","journal-title":"Polym. Prepr. (Am. Chem. Soc. Div. Polym. 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Pat. 88\u2010306393 19880713 1989;Chem. 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Poirier J.\u2010F. Carpentier Y. Sarazin unpublished results."},{"key":"e_1_2_6_113_2","unstructured":"For selected reviews see:"},{"key":"e_1_2_6_114_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-3055(08)60007-6"},{"key":"e_1_2_6_115_2","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(90)83002-2"},{"key":"e_1_2_6_116_2","unstructured":"\u00a0"},{"key":"e_1_2_6_117_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19790910124"},{"key":"e_1_2_6_117_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.197900591"},{"key":"e_1_2_6_118_2","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19811140210"},{"key":"e_1_2_6_119_2","doi-asserted-by":"publisher","DOI":"10.1021\/om980153j"},{"key":"e_1_2_6_120_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0657105"},{"key":"e_1_2_6_121_2","doi-asserted-by":"publisher","DOI":"10.1021\/om100712a"},{"key":"e_1_2_6_122_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0200747"},{"key":"e_1_2_6_123_2","unstructured":"\u00a0"},{"key":"e_1_2_6_124_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200901087"},{"key":"e_1_2_6_125_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200122m"},{"key":"e_1_2_6_126_2","unstructured":"\u00a0"},{"key":"e_1_2_6_127_2","doi-asserted-by":"publisher","DOI":"10.1021\/om010942s"},{"key":"e_1_2_6_128_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2009.01.012"},{"key":"e_1_2_6_129_2","doi-asserted-by":"publisher","DOI":"10.1039\/b515548g"},{"key":"e_1_2_6_130_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic970618i"},{"key":"e_1_2_6_131_2","unstructured":"The term \u201cpre\u2010catalyst\u201d for the Sn complexes is preferred here ahead of the more common \u201ccatalyst\u201d as they do not display significant catalytic activity in the controlled ROP ofL\u2010LA in the absence ofiPrOH. Hence iPrOH is labeled \u201cco\u2010catalyst\u201d; note that the alcohol takes the role of both the initiating group and transfer agent in these systems."},{"key":"e_1_2_6_132_2","unstructured":"\u00a0"},{"key":"e_1_2_6_133_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma048284l"},{"key":"e_1_2_6_134_2","doi-asserted-by":"publisher","DOI":"10.1021\/om200163t"},{"key":"e_1_2_6_135_2","doi-asserted-by":"publisher","DOI":"10.1039\/B919162C"},{"key":"e_1_2_6_136_2","doi-asserted-by":"publisher","DOI":"10.1039\/a703676k"},{"key":"e_1_2_6_137_2","unstructured":"With these SnIIcomplexes as well as their related Zn\u2010based complexes such as those given in reference\u2005[12c] kinetic measurements by1H\u2005NMR spectroscopy have shown that the polymerization ofL\u2010LA is fast proceeds without an induction period and is characterized by a rapid first insertion followed by a comparatively slow second insertion of the monomer whilst the polymerization of TMC presents a small induction period where the first insertion of the monomer is very slow compared to the following insertion."},{"key":"e_1_2_6_138_2","unstructured":"We are aware that the conversion of as low as 5\u201310\u2005equivalents of monomer per metal center should only yield oligomers but the term \u201cpolymerization\u201d is consistently used throughout the manuscript instead of \u201coligomerization\u201d for ease of reading."},{"key":"e_1_2_6_139_2","unstructured":"The polymerization of TMC with [TMC]0\/[3]0\/[iPrOH]0=5:1:1 required 3\u2005h to reach full conversion of the monomer in [D6]benzene at 25\u2009\u00b0C; on the other hand no reaction took place with [TMC]0\/[3]0\/[HOCH(CH3)CO2iPr]0=5:1:1 under otherwise identical conditions."},{"key":"e_1_2_6_140_2","unstructured":"On the basis of the respective pKavalues of phenols (ca. 9.90) andiPrOH (16.5) the release of {LO1}H upon treatment of compound3with even a slight excess ofiPrOH is counterintuitive on thermodynamic grounds."},{"key":"e_1_2_6_141_2","unstructured":"\u00a0"},{"key":"e_1_2_6_142_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma991751s"},{"key":"e_1_2_6_143_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.polymer.2007.05.007"},{"key":"e_1_2_6_144_2","unstructured":"Polymerizations carried out in [D8]toluene at 60\u2009\u00b0C with [L\u2010LA]0=1.0\u2009Mand [L\u2010LA]0\/[Sn]0\/[iPrOH]0=100:1:10."},{"key":"e_1_2_6_145_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00829a086"},{"key":"e_1_2_6_146_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50151a049"},{"key":"e_1_2_6_147_2","doi-asserted-by":"publisher","DOI":"10.1016\/0029-554X(69)90624-7"},{"key":"e_1_2_6_148_2","unstructured":"The identities and purities of the (micro)crystalline samples submitted for combustion analysis were established by X\u2010ray diffraction and NMR spectroscopic studies (see the Supporting Information). We are unaware of similar problems with the elemental analysis of tin\u2013amide complexes; however note that siloxy complexes6and8 which were formed directly from the treatment of compounds3and7with Ph3SiOH respectively presented satisfactory elemental analyses."},{"key":"e_1_2_6_149_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_150_2","unstructured":"\u00a0"},{"key":"e_1_2_6_151_2","unstructured":"G.\u2005M. Sheldrick SHELXS\u201097 Program for the Determination of Crystal Structures University of G\u00f6ttingen Germany 1997;"},{"key":"e_1_2_6_152_2","unstructured":"G.\u2005M. Sheldrick SHELXL\u201097 Program for the Refinement of Crystal Structures University of G\u00f6ttingen Germany 1997."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201102261","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201102261","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T10:00:38Z","timestamp":1760263238000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201102261"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2012,1,20]]},"references-count":156,"journal-issue":{"issue":"10","published-print":{"date-parts":[[2012,3,5]]}},"alternative-id":["10.1002\/chem.201102261"],"URL":"https:\/\/doi.org\/10.1002\/chem.201102261","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2012,1,20]]}}}