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The complex contains the first stable dianion of an aliphatic ketone with an electropositive metal and shows an OAd\n                    <jats:sup>2\u2212<\/jats:sup>\n                    unit with long C\u2212O bond and pyramidal carbon centre. DFT studies reveal an anionic charge on both neighbouring C and O atoms. Reductions of aliphatic ketones with magnesium(I) complexes show that these likely proceed via highly reactive dianions and afforded a 1\u2009:\u20091 mixture of an alkoxide and an enolate when an enolisable ketone was used, and rapid CH activations reactions, e.g., of stabilising ligand moieties, when non\u2010enolisable ketones were employed.\n                  <\/jats:p>","DOI":"10.1002\/anie.202204472","type":"journal-article","created":{"date-parts":[[2022,6,28]],"date-time":"2022-06-28T09:34:07Z","timestamp":1656408847000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Umpolung of an Aliphatic Ketone to a Magnesium Ketone\u20101,2\u2010diide Complex with Vicinal Dianionic Charge"],"prefix":"10.1002","volume":"61","author":[{"given":"Stuart","family":"Burnett","sequence":"first","affiliation":[{"name":"EaStCHEM School of Chemistry University of St Andrews  North Haugh St Andrews KY16 9ST UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Connor","family":"Bourne","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of St Andrews  North Haugh St Andrews KY16 9ST UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexandra M. Z.","family":"Slawin","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of St Andrews  North Haugh St Andrews KY16 9ST UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tanja","family":"van Mourik","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of St Andrews  North Haugh St Andrews KY16 9ST UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7407-8287","authenticated-orcid":false,"given":"Andreas","family":"Stasch","sequence":"additional","affiliation":[{"name":"EaStCHEM School of Chemistry University of St Andrews  North Haugh St Andrews KY16 9ST 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Deposition numbers\u20052158110 2158111 2158112 2158113 2158114 2158115 2158116 2158117 2158118 2158119 2158120 2158121 2158122 and 2158123contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_7_87_1","unstructured":"\u00a0"},{"key":"e_1_2_7_88_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CC05200K"},{"key":"e_1_2_7_89_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b06439"},{"key":"e_1_2_7_90_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200902425"},{"key":"e_1_2_7_91_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1150856"},{"key":"e_1_2_7_92_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200803960"},{"key":"e_1_2_7_92_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200803960"},{"key":"e_1_2_7_93_1","unstructured":"\u00a0"},{"key":"e_1_2_7_94_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo100953y"},{"key":"e_1_2_7_95_2","doi-asserted-by":"publisher","DOI":"10.1039\/c29690001136"},{"key":"e_1_2_7_96_1","unstructured":"\u00a0"},{"key":"e_1_2_7_97_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(00)81212-7"},{"key":"e_1_2_7_98_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00496a050"},{"key":"e_1_2_7_99_1","unstructured":"\u00a0"},{"key":"e_1_2_7_100_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3cc44509g"},{"key":"e_1_2_7_101_2","doi-asserted-by":"publisher","DOI":"10.15227\/orgsyn.060.0113"},{"key":"e_1_2_7_102_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3sc52242c"},{"key":"e_1_2_7_103_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200200584"},{"key":"e_1_2_7_104_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CC02333D"},{"key":"e_1_2_7_105_1","unstructured":"\u00a0"},{"key":"e_1_2_7_106_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41570-016-0004"},{"key":"e_1_2_7_107_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201503476"},{"key":"e_1_2_7_107_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201503476"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202204472","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.202204472","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202204472","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,17]],"date-time":"2023-08-17T10:43:21Z","timestamp":1692269001000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202204472"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,7,11]]},"references-count":112,"journal-issue":{"issue":"34","published-print":{"date-parts":[[2022,8,22]]}},"alternative-id":["10.1002\/anie.202204472"],"URL":"https:\/\/doi.org\/10.1002\/anie.202204472","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,7,11]]},"assertion":[{"value":"2022-03-26","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2022-07-11","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202204472"}}