The Aluminyl Anion: A New Generation of Aluminium Nucleophile

Abstract

Trivalent aluminium compounds are well known for their reactivity as Lewis acids/electrophiles, a feature that is exploited in many pharmaceutical, industrial and laboratory‐based reactions. Recently, a series of isolable aluminium(I) anions (“aluminyls”) have been reported, which offer an alternative to this textbook description: these reagents behave as aluminium nucleophiles. This minireview covers the synthesis, structure and reactivity of aluminyl species reported to date, together with their associated metal complexes. The frontier orbitals of each of these species have been investigated using a common methodology to allow for a like‐for‐like comparison of their electronic structure and a means of rationalising (sometimes unprecedented) patterns of reactivity.

Alkali‐Metal Mediation: Diversity of Applications in Main‐Group Organometallic Chemistry

“…Potassium is making as ignificant impact in the development of low-valent aluminium chemistry. [33][34][35][36][37][38][39][40][41] This is particularly evident in the first report of an anionic aluminium nucleophile,i nt he dimethylxanthine-supported potassium aluminyl [K{Al(NON)}] 2 (10,NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) by Goicoechea, Aldridge,and co-workers. [33] Potassium plays athreefold role,namely in the synthesis,the structure,and the reactivity of 10.The nucleophilic aluminyl anion is generated in athreestep process (Scheme 14).…”

Reactivity of a Gold-Aluminyl Complex with Carbon Dioxide: A Nucleophilic Gold?

“…Recently, a striking reactivity of CO 2 with a complex bearing a Au–Al bond has been reported. 1 A combination of the new generation aluminyl anion 2 [K{Al(NON)}] 2 with a phosphine gold t Bu 3 PAuI affords the [ t Bu 3 PAuAl(NON)] complex ( I ) which, in reaction with CO 2 (1 atm at room temperature in toluene), leads to the stable [ t Bu 3 PAuCO 2 Al(NON)] complex ( II ), where Au binds to the CO 2 carbon atom ( Scheme 1 ). This CO 2 coordination mode has been considered as the revealing of an unconventional nucleophilic behavior of gold, which, in contrast, is well-known to be an extremely powerful electrophile in organic reactions involving unsaturated CC bonds.…”

Alkalimetall‐Mediatoren: Vielfältige Anwendungen in der metallorganischen Chemie der Hauptgruppenelemente

“…Kalium hat einen bedeutenden Einfluss auf die Entwicklung der Chemie des niedervalenten Aluminiums. [33][34][35][36][37][38][39][40][41] Besonders deutlich wird dies im ersten Bericht über ein anionisches Aluminiumnukleophil, die von einem Dimethylxanthin-Liganden stabilisierte Kaliumaluminylverbindung [K{Al(NON)}] 2 (NON = 4,5-Bis(2,6-diisopropylanilido)-2,7di-tert-butyl-9,9-dimethylxanthen) 10 von Goicoechea, Aldridge et al [33] Kalium spielt bei drei Aspekten eine tragende Rolle,nämlich bei der Synthese,der Struktur und der Reaktivitätv on 10.D as nukleophile Aluminyl-Anion wird in einem dreistufigen Prozess hergestellt (Schema 14). Nach 5) ]a ufweist.…”