Reduction of CO2 with Aluminum Hydrides Supported with Ar-BIAN Radical-Anions (Ar-BIAN = 1,2-Bis(arylimino)acenaphthene)

Tatyana S Koptseva; Mikhail V Moskalev; Alexandra A Skatova; Roman V Rumyantcev; Igor L Fedushkin

doi:10.1021/acs.inorgchem.1c02731

Reduction of CO₂ with Aluminum Hydrides Supported with Ar-BIAN Radical-Anions (Ar-BIAN = 1,2-Bis(arylimino)acenaphthene)

Inorg Chem. 2022 Jan 10;61(1):206-213. doi: 10.1021/acs.inorgchem.1c02731. Epub 2021 Dec 23.

Authors

Tatyana S Koptseva¹, Mikhail V Moskalev¹, Alexandra A Skatova¹, Roman V Rumyantcev¹, Igor L Fedushkin¹

Affiliation

¹ G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina street 49, 603950, Nizhny Novgorod, Russian Federation.

PMID: 34949085
DOI: 10.1021/acs.inorgchem.1c02731

Abstract

The reactions of H₂AlCl with [(dpp-Bian)Na(Et₂O)_n] and [(Ar^BIG-Bian)Na(THF)] produce respective aluminum hydrides supported by radical-anionic 1,2-bis(arylimino)acenaphthene ligands, [(dpp-Bian)AlH₂] (1) and [(Ar^BIG-Bian)AlH₂(THF)] (2) (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene); Ar^BIG-Bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene). The reaction of 1 with CO₂ proceeds with reduction of both C═O bonds and results in diolate [{(dpp-Bian)Al(μ-O₂CH₂)}₂] (3). Complex 2 reacts with CO₂ to carbonate [{(Ar^BIG-Bian)Al(μ-OCH₂OCO₂)}₂] (4) that is a result of the insertion of CO₂ into the Al-O bond in diolate species formed initially. Aluminum monohydrides [(dpp-Bian)AlH(X)] (X = Cl, 5; Me, 6) react with CO₂ to form respective alumoxanes [{(dpp-Bian)AlX}₂(μ-O)] (X = Cl, 7 and X = Me, 8). Compounds 1-4, 7, and 8 have been characterized by ESR and IR spectroscopy, and their molecular structures have been determined by single-crystal X-ray analysis.