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Complexes <jats:bold>5<\/jats:bold> and <jats:bold>6<\/jats:bold> are readily available through an alcoholysis reaction between BnOH and the corresponding Zn\u2013NHC ethyl species [(<jats:italic>S<\/jats:italic>,<jats:italic>C<\/jats:italic><jats:sub>NHC<\/jats:sub>)ZnCl(Et)] (<jats:bold>3<\/jats:bold>) and [(<jats:italic>O<\/jats:italic>,<jats:italic>C<\/jats:italic><jats:sub>NHC<\/jats:sub>)ZnCl(Et)] (<jats:bold>4<\/jats:bold>), and species <jats:bold>3<\/jats:bold> and <jats:bold>4<\/jats:bold> were obtained from the reaction of ZnEt<jats:sub>2<\/jats:sub> with the <jats:italic>N<\/jats:italic>\u2010methyl\u2010<jats:italic>N<\/jats:italic>'\u2010ethylphenylsulfide (<jats:bold>1\u22c5<\/jats:bold>HCl) and <jats:italic>N<\/jats:italic>\u2010methyl\u2010<jats:italic>N<\/jats:italic>'\u2010ethylmethylether (<jats:bold>2\u22c5<\/jats:bold>HCl) imidazolium salts, respectively. Both solution and solid\u2010state structural data for Zn benzyloxide species <jats:bold>5<\/jats:bold> and <jats:bold>6<\/jats:bold> agree with dimeric structures under the studied conditions (reaction conditions: CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub> or THF, room temperature). A computational analysis of species <jats:bold>3<\/jats:bold> and <jats:bold>4<\/jats:bold> supports a dimeric structure in solution. The Zn<jats:sup>II<\/jats:sup> alkoxide species <jats:bold>5<\/jats:bold> and <jats:bold>6<\/jats:bold> were found to mediate either the ROP of lactide (in an effective and controlled manner) to produce chain length\u2010controlled polylactide (PLA) or, in the presence of an alcohol source such as MeOH, the controlled degradation of PLA through extensive transesterification reactions to afford methyl lactate as the major product. A thorough DFT computational analysis of the ROP of lactide initiated by complex <jats:bold>5<\/jats:bold> was performed, which revealed that the operating coordination\u2013insertion mechanism was assisted by the second Zn center, leading to a lower\u2010energy ROP process; this result may be of interest for the future design of well\u2010defined and high\u2010performance metal\u2010based catalysts.<\/jats:p>","DOI":"10.1002\/cctc.201301015","type":"journal-article","created":{"date-parts":[[2014,3,5]],"date-time":"2014-03-05T02:27:11Z","timestamp":1393986431000},"page":"1357-1367","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":82,"title":["Dinuclear Zinc\u2013N\u2010Heterocyclic Carbene Complexes for Either the Controlled Ring\u2010Opening Polymerization of Lactide or the Controlled Degradation of Polylactide Under Mild Conditions"],"prefix":"10.1002","volume":"6","author":[{"given":"Christophe","family":"Fliedel","sequence":"first","affiliation":[]},{"given":"Diogo","family":"Vila\u2010Vi\u00e7osa","sequence":"additional","affiliation":[]},{"given":"Maria Jos\u00e9","family":"Calhorda","sequence":"additional","affiliation":[]},{"given":"Samuel","family":"Dagorne","sequence":"additional","affiliation":[]},{"given":"Teresa","family":"Avil\u00e9s","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2014,3,5]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/b811392k"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.addr.2008.02.008"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.progpolymsci.2007.05.017"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/bm0494702"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/bm034247a"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr940351u"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.19960080406"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/b820162p"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma801735u"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1080\/15583720701834133"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1114736"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200301655"},{"key":"e_1_2_6_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200301655"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1007\/3-540-45734-8_5"},{"key":"e_1_2_6_16_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_17_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.biortech.2010.05.092"},{"key":"e_1_2_6_18_2","unstructured":"\u00a0"},{"key":"e_1_2_6_19_2","unstructured":"P. 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