Abstract
Dialumenes are neutral AlI compounds with Al=Al multiple bonds. We report the isolation of an amidophosphine‐supported dialumene. Our X‐ray crystallographic, spectroscopic, and computational DFT analyses reveal a long and extreme trans‐bent Al=Al bond with a low dissociation energy and bond order. In solution, the dialumene can dissociate into monomeric AlI species. Reactivity studies reveal two modes of reaction: as dialumene or as aluminyl monomers.
Highlights
Like other low oxidation-state main group systems, AlI compounds are revealing potential in bond-activation and catalysis.[1]
Dialumenes can be divided into two classes: basecoordinated dialumenes (R(L)Al=Al(L)R), which are isoelectronic with alkenes, and “transient” dialumenes (RAl=AlR)
Trans-bend angles and Si=Si bond distances are correlated with the singlet-triplet energy gap (DES-T) of the notional or real silylene monomers, DSiR2.[17]. We find that the same relationship applies to dialumenes: Al=Al bond dissociation energy increases as DES-T for the monomeric R(L)AlD fragments decreases (Figure S11)
Summary
Like other low oxidation-state main group systems, AlI compounds are revealing potential in bond-activation and catalysis.[1] Dialumenes are neutral AlI compounds with Al=Al multiple bonds They sit alongside the prototypical neutral AlI compounds (Cp*Al) and NacNacAl(I), and the rapidly developing class of anionic aluminyl compounds.[2]. Donor-free dialumenes III feature low Al=Al bond orders and substantially trans-bent geometry.[8] These dialumenes can dissociate readily in solution; V appears to react as either RAl=AlR or RAlD species.[9] Recently, Power showed that a larger terphenyl substituent allows access to an RAlD monomer rather than IV.[10]. Angewandte Chemie International Edition published by Wiley-VCH GmbH 1 dissociates and can react as either dialumene or monomeric aluminyl
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
