Synthesis of a low-valent Al₄⁺ cluster cation salt

Low-valent aluminium compounds are very reactive main-group species and have therefore been widely investigated. Since the isolation of a stable molecular Al(I) compound in 1991, [(AlCp*)₄] (Cp* = [C₅Me₅]^-), a variety of highly reactive neutral or anionic low-valent aluminium complexes have been developed. By contrast, their cationic counterparts have remained difficult to access. Here, we report the synthesis of [Al(AlCp*)₃]⁺[Al(OR^F)₄]^- (R^F = C(CF₃)₃) through a simple metathesis reaction between [(AlCp*)₄] and Li[Al(OR^F)₄]. Unexpectedly, the [Al(AlCp*)₃]⁺ salt forms a dimer in the solid state and concentrated solutions. Addition of Lewis bases results in monomerization and coordination to the unique formal Al⁺ atom, giving [(L)_xAl(AlCp*)₃]⁺ salts where L is hexaphenylcarbodiphosphorane (x = 1), tetramethylethylenediamine (x = 1) or 4-dimethylaminopyridine (x = 3). The Al⁺-Al_Cp* bonds in the resulting [(L)_xAl(AlCp*)₃]⁺ cluster cations can be finely tuned between very strong (with no ligand L) to very weak and approaching isolated [Al(L)₃]⁺ ions (when L is dimethylaminopyridine).