Francis Maria, Shinde Kishor, Roy Sudipta
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati Tirupati 517619 Andhra Pradesh India
RSC Adv. 2025 Mar 25;15(12):9208-9215. doi: 10.1039/d5ra00211g. eCollection 2025 Mar 21.
Herein, we depict the stability, and bonding studies of bis-(dichloro-aluminium) oxides ClAl-O-AlCl supported by a pair of homo-/hetero-leptic donor base ligands L, L' [L, L' = cyclic alkyl(amino) carbene (cAAC; 1); N-heterocyclic carbene (NHC; 2); di-amido carbene (DAC; 3); L = cAAC, L' = NHC; (4)] with a general formula (L)Al(Cl)-O-Al(Cl)(L') (1-4) by NBO, QTAIM and EDA-NOCV analyses. Theoretical calculations suggest that 1-4 possess favorable interaction energies (Δ ), and bond dissociation energies between L/L', and Al(Cl)-O-Al(Cl) fragments 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)-O-Al(Cl)(cAAC) (1') by reacting cAAC and AlCl in the presence of a controlled amount of HO, 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.
在此，我们通过自然键轨道（NBO）、量子拓扑原子理论（QTAIM）和能量分解分析-自然轨道耦合簇方法（EDA-NOCV）分析，描述了由一对同配/异配给体碱配体L、L'[L、L' = 环烷基（氨基）卡宾（cAAC；1）；N-杂环卡宾（NHC；2）；二氨基卡宾（DAC；3）；L = cAAC，L' = NHC；（4）]支撑的双（二氯铝）氧化物ClAl-O-AlCl，其通式为（L）Al（Cl）-O-Al（Cl）（L'）（1-4）的稳定性和键合研究。理论计算表明，1-4具有良好的相互作用能（Δ），以及L/L'与Al（Cl）-O-Al（Cl）片段之间的键解离能，形成了两个配位L→Al键[1 > 4 > 2 > 3]。这种趋势通过配体L/L'的σ供体能力得到合理解释。此外，我们描述了通过在可控量的HO存在下使cAAC与AlCl反应，首次成功固态分离无色化合物（cAAC）Al（Cl）-O-Al（Cl）（cAAC）（1'），其中使用两当量的cAAC作为碱。1'已通过单晶X射线衍射进行结构表征，并通过核磁共振光谱进一步研究。
