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The synthesized inverse\u2010sandwich complexes [{(Me<jats:sub>3<\/jats:sub>Si)<jats:sub>2<\/jats:sub>NC(N<jats:sup>i<\/jats:sup>Pr)<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>RE]<jats:sub>2<\/jats:sub>(\u03bc\u2010\u03b7<jats:sup>6<\/jats:sup>\u2009:\u2009\u03b7<jats:sup>6<\/jats:sup>\u2010C<jats:sub>6<\/jats:sub>H<jats:sub>6<\/jats:sub>), (RE=Y (<jats:bold>1<\/jats:bold>), Dy (<jats:bold>2<\/jats:bold>), and Er (<jats:bold>3<\/jats:bold>)) were crystallized from aprotic solvents and feature a remarkably planar parent benzene dianion, previously not encountered for any metal ion prone to low or absent covalency. The \u22122 charge localization at the benzene ligand was deduced from the results obtained by single\u2010crystal X\u2010ray diffraction analyses, spectroscopy, magnetometry, and Density Functional Theory (DFT) calculations. In the <jats:sup>1<\/jats:sup>H NMR spectrum of the diamagnetic Y complex <jats:bold>1<\/jats:bold>, the equivalent proton resonance of the bridging benzene dianion ligand is drastically shifted to higher field in comparison to free benzene. This and the calculated highly positive Nucleus\u2010Independent Chemical Shift (NICS) values are attributed to the antiaromatic character of the benzene dianion ligand. The crucial role of the ancillary guanidinate ligand scaffold in stabilizing the planar benzene dianion conformation was also elucidated by DFT calculations. Remarkably, the planarity of the benzene dianion originates from the stabilization of the \u03c0\u2010type orbitals of the d\u2010manifold and compression through its strong electrostatic interaction with the two RE<jats:sup>III<\/jats:sup> sites.<\/jats:p>","DOI":"10.1002\/anie.202417217","type":"journal-article","created":{"date-parts":[[2024,10,14]],"date-time":"2024-10-14T03:10:26Z","timestamp":1728875426000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Stabilization of the Compressed Planar Benzene Dianion in Inverse\u2010Sandwich Rare Earth Metal Complexes"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7509-4502","authenticated-orcid":false,"suffix":"IV","given":"Francis","family":"Delano","sequence":"first","affiliation":[{"name":"Department of Chemistry Michigan State University  578 South Shaw Lane East Lansing, Michigan 48824 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7983-9850","authenticated-orcid":false,"given":"Selvan","family":"Demir","sequence":"additional","affiliation":[{"name":"Department of Chemistry Michigan State University  578 South Shaw Lane East Lansing, Michigan 48824 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,12,5]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0306790"},{"key":"e_1_2_8_2_1","first-page":"98","volume":"3","author":"Kekul\u00e9 A.","year":"1865","journal-title":"Bull. 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