| Autor: |
Dabringhaus, Philipp, Willrett, Julie, Krossing, Ingo |
| Zdroj: |
Nature Chemistry; 20220101, Issue: Preprints p1-7, 7p |
| Abstrakt: |
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(ORF)4]–(RF= C(CF3)3) through a simple metathesis reaction between [(AlCp*)4] and Li[Al(ORF)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+–AlCp*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). |
| Databáze: |
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