Comproportionation of a dialuminyne with alane or dialane dihalides as a clean route to dialuminenes

Abstract

Dialuminenes RAlAlR (R = m-terphenyl or bulky aryl) react with the aromatic solvents (e.g. benzene or toluene) in which they dissolve. We synthesized -SiMe3 substituted derivatives of known terphenyl ligands...

Dearomatization of C6 Aromatic Hydrocarbons by Main Group Complexes

“…Compound 43 b can act as a masked dialumene that was revealed by the exchange reactions of 43 b with C 6 D 6 , naphthalene, anthracene and bis(trimethylsilyl)acetylene at room temperature forming the corresponding trapping products, dialumene‐C 6 D 6 , ‐naphthalene or ‐anthracene adduct or 1,2‐dialuminacyclobutene, respectively. The Power group also prepared a similar dialumene‐benzene adduct 43 c by the reaction of dianionic dialuminyne 40 with 39 c or 41 in benzene, whereas 43 c was not obtained in the reduction of the corresponding 1,2‐diiododialane 39 c (Scheme 5a) [34] . In 2018, the Harder group reported facile benzene reduction by Ca 2+ /Al I Lewis Acid/Base Combination (Scheme 5b).…”

“…The Power group also prepared a similar dialumene-benzene adduct 43 c by the reaction of dianionic dialuminyne 40 with 39 c or 41 in benzene, whereas 43 c was not obtained in the reduction of the corresponding 1,2-diiododialane 39 c (Scheme 5a). [34] In 2018, the Harder group reported facile benzene reduction by Ca 2 + /Al I Lewis Acid/Base Combination (Scheme 5b). Treatment of alumylene stabilized by a β-diketiminate ligand 44 with [(BDI)Ca + • C 6 H 6 ][B(C 6 F 5 )4 À ] 45 in benzene/fluorobenzene (4 : 1) at room temperature resulted in the formation of a [1 + 4] cycloaddition product 46, in which aluminanorbornadiene strongly coordinates to the Ca 2 + metal ion.…”

Reduction and Cycloaddition of Heteroalkenes at Ga(I) Bisamide Center

“…Despite structural and electronic differences, all the aforementioned metallylenes can undergo cycloadditions [55]. Dialumenes, reminiscent of olefins (Scheme 2, A), unveil their intriguing propensity for [2+2] cycloaddition reactions with an array of substratesranging from CO 2 [56], olefins, and alkynes [57,58] to unactivated benzene rings [59,60]. Gallium terphenyl dimetallene ArGaGaAr (Ar = 2,6-terphenyl) was reported to react under ambient conditions with ethylene, propene, 1-hexene, and styrene to give 1,4digallacycloalkanes [61].…”