Reaction of an Al-centered anion with toluene proceeded to form CÀH cleaved product with a perfect metaselectivity and a relatively small kinetic isotope effect (KIE, k H / k D = 1.51). DFT calculations suggested a two-step reaction mechanism and electronically controlled meta-selectivity arising from the electron-donating methyl group. The reaction with other mono-substituted arenes was also investigated.

The reactivity of dialkylalumanyl anion (1) towards naphthalene, anthracene, diphenylacetylene, and (E)/(Z)‐stilbenes was investigated. The compound 1 reacts with naphthalene and anthracene through (1+4) cyclization, giving Al‐containing norbornadiene derivatives. In the reaction of 1 with diphenylacetylene and (E)/(Z)‐stilbenes, (1+2) cyclization proceeded to form Al‐C‐C three‐membered rings. Cyclization toward (E)‐ or (Z)‐stilbenes solely gave a trans‐cycloadduct. DFT calculations revealed that the cycloaddition of 1 with (Z)‐stilbene proceeds via a single transition state with a carbanion character, which results in the selectivity towards the trans‐cycloadduct.

The reaction between a dialkyl‐substituted alumanyl anion and [Y(CH2SiMe3)2(thf)3][BPh4] resulted in the formation of (dialkylalumanyl)yttrium complex 2, which exhibits the first 2‐center–2‐electron (2 c‐2 e) Al−Y bond. The 1H and 13C NMR spectra of 2 together with an X‐ray crystallographic analysis indicated a C2v symmetrical structure. DFT calculations on 2 revealed that its LUMO consists of overlapping 3 p‐ and 4 d‐orbitals of the Al and Y atoms, respectively, and that the HOMO–LUMO gap is narrow. The UV/Vis spectrum of 2 exhibited a visible absorption at 432 nm, which suggests that the strong σ‐donating and π‐accepting character of the three‐coordinate dialkylalumanyl ligand generates a colored d0‐complex that does not contain any π‐electrons.

Ruthenium-catalyzed annulation of 1-naphthylsilanes with internal alkynes afforded silaphenalenes through cleavage of the C-H bond at the 8-position of the naphthalene. [RuH2 (CO){P(p-FC6 H4 )3 }3 ] efficiently catalyzed the reaction. The use of 1-naphthyldiphenylsilane as a substrate resulted in a better yield of the annulation product compared to the use of silanes with alkyl groups on the silicon atom. Internal alkynes with both aryl and alkyl groups were tolerated in this reaction.

A reaction of dialkylalumanylpotassium with Ti­(O i Pr)4 was investigated. The alumanyl anion worked as a reducing reagent to afford the trivalent titanium complex as a contact ion pair with aluminate anion probably via single-electron transfer. The ESR spectrum revealed the delocalization of an unpaired electron over Ti and Al atoms. The DFT calculations provided information about the ratio of unpaired electrons on Ti and Al atoms and the UV–vis absorption spectrum.