{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T19:03:56Z","timestamp":1790708636662,"version":"4.1.0"},"reference-count":42,"publisher":"Wiley","issue":"44","license":[{"start":{"date-parts":[[2015,9,11]],"date-time":"2015-09-11T00:00:00Z","timestamp":1441929600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100000923","name":"Australian Research Council","doi-asserted-by":"crossref","id":[{"id":"10.13039\/501100000923","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2015,10,26]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The first examples of magnesium(I) dimers bearing tripodal ligands, [(Mg{\u03ba<jats:sup>3<\/jats:sup>\u2010<jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2032,<jats:italic>O<\/jats:italic>\u2010(ArNCMe)<jats:sub>2<\/jats:sub>(OCCPh<jats:sub>2<\/jats:sub>)CH})<jats:sub>2<\/jats:sub>] [Ar=2,6\u2010<jats:italic>i<\/jats:italic>Pr<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub> (Dip) <jats:bold>7<\/jats:bold>, 2,6\u2010Et<jats:sub>2<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>3<\/jats:sub> (Dep) <jats:bold>8<\/jats:bold>, or mesityl (Mes) <jats:bold>9<\/jats:bold>] have been prepared by post\u2010synthetic modification of the \u03b2\u2010diketiminato ligands of previously reported magnesium(I) systems, using diphenylketene, O\uf8feC\uf8feCPh<jats:sub>2<\/jats:sub>. In contrast, related reactions between \u03b2\u2010diketiminato magnesium(I) dimers and the isoelectronic ketenimine, MesN\uf8feC\uf8feCPh<jats:sub>2<\/jats:sub>, resulted in reductive insertion of the substrate into the Mg\uf8ffMg bond of the magnesium(I) reactant, and formation of [{(Nacnac)Mg}<jats:sub>2<\/jats:sub>{\u03bc\u2010\u03ba<jats:sup>2<\/jats:sup>\u2010<jats:italic>N<\/jats:italic>,<jats:italic>C<\/jats:italic>\u2010(Mes)NCCPh<jats:sub>2<\/jats:sub>}] (Nacnac=[(ArNCMe)<jats:sub>2<\/jats:sub>CH]<jats:sup>\u2212<\/jats:sup>; Ar=Dep <jats:bold>10<\/jats:bold> or Mes <jats:bold>11<\/jats:bold>). Reactions of the four\u2010coordinate magnesium(I) dimer <jats:bold>8<\/jats:bold> with excess CO<jats:sub>2<\/jats:sub> are readily controlled, and cleanly give carbonate [(LMg)<jats:sub>2<\/jats:sub>(\u03bc\u2010\u03ba<jats:sup>2<\/jats:sup>:\u03ba<jats:sup>2<\/jats:sup>\u2010CO<jats:sub>3<\/jats:sub>)] <jats:bold>12<\/jats:bold> (L=[\u03ba<jats:sup>3<\/jats:sup>\u2010<jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2032,<jats:italic>O<\/jats:italic>\u2010(DepNCMe)<jats:sub>2<\/jats:sub>(OCCPh<jats:sub>2<\/jats:sub>)CH]<jats:sup>\u2212<\/jats:sup>; thermodynamic product), or oxalate [(LMg)<jats:sub>2<\/jats:sub>(\u03bc\u2010\u03ba<jats:sup>2<\/jats:sup>:\u03ba<jats:sup>2<\/jats:sup>\u2010C<jats:sub>2<\/jats:sub>O<jats:sub>4<\/jats:sub>)] <jats:bold>13<\/jats:bold> (kinetic product), depending on the reaction temperature. Compound <jats:bold>12<\/jats:bold> and CO are formed by reductive disproportionation of CO<jats:sub>2<\/jats:sub>, whereas <jats:bold>13<\/jats:bold> results from reductive coupling of two molecules of the gas. Treatment of <jats:bold>8<\/jats:bold> with an excess of N<jats:sub>2<\/jats:sub>O cleanly gives the \u03bc\u2010oxo complex [(LMg)<jats:sub>2<\/jats:sub>(\u03bc\u2010O)] <jats:bold>14<\/jats:bold>, which reacts facilely with CO<jats:sub>2<\/jats:sub> to give <jats:bold>12<\/jats:bold>. This result presents the possibility that <jats:bold>14<\/jats:bold> is an intermediate in the formation of <jats:bold>12<\/jats:bold> from the reaction of <jats:bold>8<\/jats:bold> and CO<jats:sub>2<\/jats:sub>. In contrast to its reactions with CO<jats:sub>2<\/jats:sub>, <jats:bold>8<\/jats:bold> reacts with SO<jats:sub>2<\/jats:sub> over a wide temperature range to give only one product; the first example of a magnesium dithionite complex, [(LMg)<jats:sub>2<\/jats:sub>(\u03bc\u2010\u03ba<jats:sup>2<\/jats:sup>:\u03ba<jats:sup>2<\/jats:sup>\u2010S<jats:sub>2<\/jats:sub>O<jats:sub>4<\/jats:sub>)] <jats:bold>16<\/jats:bold>, which is formed by reductive coupling of two molecules of SO<jats:sub>2<\/jats:sub>, and is closely related to f\u2010block metal dithionite complexes derived from similar SO<jats:sub>2<\/jats:sub> reductive coupling processes. On the whole, this study strengthens previously proposed analogies between the reactivities of magnesium(I) systems and low\u2010valent f\u2010block metal complexes, especially with respect to small molecule activations.<\/jats:p>","DOI":"10.1002\/chem.201502755","type":"journal-article","created":{"date-parts":[[2015,9,11]],"date-time":"2015-09-11T04:29:54Z","timestamp":1441945794000},"page":"15749-15758","source":"Crossref","is-referenced-by-count":80,"title":["Magnesium(I) Dimers Bearing Tripodal Diimine\u2013Enolate Ligands: Proficient Reagents for the Controlled Reductive Activation of CO<sub>2<\/sub> and SO<sub>2<\/sub>"],"prefix":"10.1002","volume":"21","author":[{"given":"Aaron J.","family":"Boutland","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Indrek","family":"Pernik","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andreas","family":"Stasch","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Cameron","family":"Jones","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2015,9,11]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1150856"},{"key":"e_1_2_6_2_2","unstructured":"\u00a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-642-36270-5_3"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0dt01831g"},{"key":"e_1_2_6_5_2","unstructured":"\u00a0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b06439"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200902425"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200803960"},{"key":"e_1_2_6_8_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200803960"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201404284"},{"key":"e_1_2_6_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201404284"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja900568c"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3sc52242c"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4CC04984E"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2011.07.015"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1039\/b611784h"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic971381t"},{"key":"e_1_2_6_16_2","unstructured":"\u00a0"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc34150f"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/b927142b"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja053497r"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1102602"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/b815576c"},{"key":"e_1_2_6_22_2","unstructured":"\u00a0"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201201030"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200900331"},{"key":"e_1_2_6_24_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200900331"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4SC00885E"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic034853e"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp5104998"},{"key":"e_1_2_6_28_2","unstructured":"\u00a0"},{"key":"e_1_2_6_29_2","unstructured":"S.\u2005V. 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