Activation of Dihydrogen by Masked Doubly Bonded Aluminum Species

• Published in: Angewandte Chemie International Edition Vol. 55; no. 41; pp. 12877 - 12880
• Main Authors: Nagata, Koichi, Murosaki, Takahiro, Agou, Tomohiro, Sasamori, Takahiro, Matsuo, Tsukasa, Tokitoh, Norihiro
• Format: Journal Article
• Language: English
• Published: Germany Blackwell Publishing Ltd 04.10.2016; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Activation; Aluminum; aluminum hydride; Aromatic compounds; Crystal structure; dialumene; Dimers; hydrogen; hydrogen activation; Species; Temperature effects; aluminum hydride; aluminum; hydrogen; dialumene; hydrogen activation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201606684

Activation of dihydrogen by masked dialumenes (Al=Al doubly bonded species) is reported. Reactions of barrelene‐type dialumanes, which have the reactivity as masked equivalents of 1,2‐diaryldialumenes ArAl=AlAr, with H2 afforded dihydroalumanes ArAlH2 at room temperature (Ar: bulky aryl groups). These dihydroalumanes form hydrogen‐bridged dimers [ArHAl(μ‐H)]2 in the crystalline state, while a monomer–dimer equilibrium was suggested in solution. The 1,2‐diaryldialumenes generated from the barrelene‐type dialumanes are the putative active species in the cleavage of H2. Cut in half by the masked magician: Homolytic dihydrogen splitting was achieved by using barrelene‐type dialumanes which serve as masked Al=Al doubly bonded species under ambient conditions. The generated dihydroalumane dimers are presumably in equilibrium with the corresponding monomers in solution.