Theoretical and experimental studies on stability, bonding and isolation of elusive bis-(dichloro-aluminium) oxides supported by donor-base ligands

对由供体碱配体支撑的难以捉摸的双(二氯铝)氧化物的稳定性、键合和分离的理论和实验研究

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Abstract

Herein, we depict the stability, and bonding studies of bis-(dichloro-aluminium) oxides Cl(2)Al-O-AlCl(2) supported by a pair of homo-/hetero-leptic donor base ligands L, L' [L, L' = cyclic alkyl(amino) carbene (cAAC(Me); 1); N-heterocyclic carbene (NHC(Me); 2); di-amido carbene (DAC(Me); 3); L = cAAC(Me), L' = NHC(Me); (4)] with a general formula (L)Al(Cl)(2)-O-Al(Cl)(2)(L') (1-4) by NBO, QTAIM and EDA-NOCV analyses. Theoretical calculations suggest that 1-4 possess favorable interaction energies (ΔE (int)), and bond dissociation energies between L/L', and Al(Cl)(2)-O-Al(Cl)(2) fragments via the formation of two dative L→Al bonds [1 > 4 > 2 > 3]. This trend is rationalized by the σ-donor ability of the ligands L/L'. Moreover, we depict the first successful solid-state isolation of the colorless compound (cAAC)Al(Cl)(2)-O-Al(Cl)(2)(cAAC) (1') by reacting cAAC and AlCl(3) in the presence of a controlled amount of H(2)O, where two equiv. of cAAC is being utilized as the base. 1' has been structurally characterized by single-crystal X-ray diffraction, and further studied by NMR spectroscopy.

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