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Direct H<jats:sub>2<\/jats:sub> hydrogenation of the heavier analogues (AM=Rb, Cs) produced the first examples of structurally characterized rubidium and caesium dihydridoaluminates, although harsh conditions were required for complete conversion. Using 1,4\u2010cyclohexadiene (1,4\u2010CHD) as an alternative hydrogen source in transfer hydrogenation reactions provided a lower energy pathway to the full series of products for AM=Li\u2212Cs. A further moderation in conditions was noted for the thermal decomposition of the (silyl)(hydrido)aluminates, AM[Al(NON<jats:sup>Dipp<\/jats:sup>)(H)(SiH<jats:sub>2<\/jats:sub>Ph)]. Probing the reaction of Cs[Al(NON<jats:sup>Dipp<\/jats:sup>)] with 1,4\u2010CHD provided access to a novel inverse sandwich complex, [{Cs(Et<jats:sub>2<\/jats:sub>O)}<jats:sub>2<\/jats:sub>{Al(NON<jats:sup>Dipp<\/jats:sup>)(H)}<jats:sub>2<\/jats:sub>(C<jats:sub>6<\/jats:sub>H<jats:sub>6<\/jats:sub>)], containing the 1,4\u2010dialuminated [C<jats:sub>6<\/jats:sub>H<jats:sub>6<\/jats:sub>]<jats:sup>2\u2212<\/jats:sup> dianion and representing the first time that an intermediate in the commonly utilized oxidation process of 1,4\u2010CHD to benzene has been trapped. The synthetic utility of the newly installed Al\u2212H bonds has been demonstrated by their ability to reduce CO<jats:sub>2<\/jats:sub> under mild conditions to form the bis\u2010formate AM[Al(NON<jats:sup>Dipp<\/jats:sup>)(O<jats:sub>2<\/jats:sub>CH)<jats:sub>2<\/jats:sub>] compounds, which exhibit a diverse series of eyecatching bimetallacyclic structures.<\/jats:p>","DOI":"10.1002\/chem.202301849","type":"journal-article","created":{"date-parts":[[2023,7,10]],"date-time":"2023-07-10T22:29:15Z","timestamp":1689028155000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Three Oxidative Addition Routes of Alkali Metal Aluminyls to Dihydridoaluminates and Reactivity with CO<sub>2<\/sub>"],"prefix":"10.1002","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0925-9276","authenticated-orcid":false,"given":"Sumanta","family":"Banerjee","sequence":"first","affiliation":[{"name":"WestCHEM Department of Pure and Applied Chemistry University of Strathclyde  G1\u20091XL Glasgow UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gerd M.","family":"Ballmann","sequence":"additional","affiliation":[{"name":"WestCHEM Department of Pure and Applied Chemistry University of Strathclyde  G1\u20091XL Glasgow UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5383-3220","authenticated-orcid":false,"given":"Matthew J.","family":"Evans","sequence":"additional","affiliation":[{"name":"School of Chemical and Physical Sciences Victoria University of Wellington  P.O. Box 600 Wellington 6140 New Zealand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrea","family":"O'Reilly","sequence":"additional","affiliation":[{"name":"School of Chemical and Physical Sciences Victoria University of Wellington  P.O. Box 600 Wellington 6140 New Zealand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3652-6015","authenticated-orcid":false,"given":"Alan R.","family":"Kennedy","sequence":"additional","affiliation":[{"name":"WestCHEM Department of Pure and Applied Chemistry University of Strathclyde  G1\u20091XL Glasgow UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6370-6452","authenticated-orcid":false,"given":"J. Robin","family":"Fulton","sequence":"additional","affiliation":[{"name":"School of Chemical and Physical Sciences Victoria University of Wellington  P.O. 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