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Cationic dialanes with fluxional π-bridged cyclopentadienyl ligands† Philipp Dabringhaus, a Silja Zedlitza and Ingo Krossing*a Abstract Unique π-cyclopentadienyl bridged dialanes are synthesized as complex salts with aluminate anions by comproportionation of aluminocenium cations [AlIII(Cp)(Cp*)]+/[AlIIICp2]+ with [(AlICp*)4]. Very short Al–Al bond lengths occur in positively charged Al24+ fragments.
EDA-NOCV-Analyses To further investigate the bonding situation in 4, the Si−Al bonds were studied by EDA-NOCV analyses (Figure 5; Supporting Information, section 2). For the bridging AlCp* units, only minimal differences in energy are computed for a heterolytic fragmentation into singlet or the alternative homolytic fragmentation into triplet fragments (heterolytic: ΔEOrb(1)=−244.57 kcal mol−1, homolytic: ΔEOrb(1)=−238.04 kcal mol−1, see Figure 5a and Table S5).
Cationic Dialanes with Fluxional π-Bridged Cyclopentadienyl Ligands Philipp Dabringhaus, Silja Zedlitz and Ingo Krossing Abstract Unique π-cyclopentadienyl-bridged dialanes are synthesized as complex salts with aluminate anions by comproportionation of alu-minocenium cations [AlIII(Cp)(Cp*)]+ /[AlIIICp2]+ with [(AlICp*)4]. Very short Al–Al bond lengths occur in the positively charged Al24+ fragments.
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