Three oxidative addition routes of alkali metal aluminyls to dihydroaluminates and reactivity with CO2
Banerjee, Sumanta and Ballmann, Gerd M. and Evans, Matthew J. and O'Reilly, Andrea and Kennedy, Alan R. and Fulton, J. Robin and Coles, Martyn P. and Mulvey, Robert E. (2023) Three oxidative addition routes of alkali metal aluminyls to dihydroaluminates and reactivity with CO2. Chemistry - A European Journal, 29 (56). e202301849. ISSN 1521-3765 (https://doi.org/10.1002/chem.202301849)
Preview |
Text.
Filename: Banerjee_etal_CEJ_2023_Three_oxidative_addition_routes_of_group_one_aluminyls.pdf
Final Published Version License: Download (1MB)| Preview |
Abstract
Three distinct routes are reported to the soluble, dihydridoaluminate compounds, AM[Al(NONDipp)(H)2] (AM = Li, Na, K, Rb, Cs; [NONDipp]2– = [O(SiMe2NDipp)2]2–; Dipp = 2,6-iPr2C6H3) starting from the alkali metal aluminyls, AM[Al(NONDipp)]. Direct H2 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-cyclohexadiene (1,4-CHD) as an alternative hydrogen source in transfer hydrogenation reactions provided a lower energy pathway to the full series of products for AM = Li – Cs. A further moderation in conditions was noted for the thermal decomposition of the (silyl)(hydrido)aluminates, AM[Al(NONDipp)(H)(SiH2Ph)]. Probing the reaction of Cs[Al(NONDipp)] with 1,4-CHD provided access to a novel inverse sandwich complex, [{Cs(Et2O)}2{Al(NONDipp)(H)}2(C6H6)], containing the 1,4-dialuminated [C6H6]2– dianion and representing the first time that an intermediate in the commonly utilized oxidation process of 1,4-CHD to benzene has been trapped. The synthetic utility of the newly installed Al–H bonds has been demonstrated by their ability to reduce CO2 under mild conditions to form the bis-formate AM[Al(NONDipp)(O2CH)2] compounds, which exhibit a diverse series of eyecatching bimetallacyclic structures.
ORCID iDs
Banerjee, Sumanta, Ballmann, Gerd M., Evans, Matthew J., O'Reilly, Andrea, Kennedy, Alan R. ORCID: https://orcid.org/0000-0003-3652-6015, Fulton, J. Robin, Coles, Martyn P. and Mulvey, Robert E. ORCID: https://orcid.org/0000-0002-1015-2564;-
-
Item type: Article ID code: 86161 Dates: DateEvent9 October 2023Published10 July 2023Published Online10 July 2023AcceptedSubjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 18 Jul 2023 13:48 Last modified: 03 Oct 2024 00:41 URI: https://strathprints.strath.ac.uk/id/eprint/86161