Griffin Liam P, Ellwanger Mathias A, Crumpton Agamemnon E, Roy Matthew M D, Heilmann Andreas, Aldridge Simon
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Angew Chem Int Ed Engl. 2024 Jun 3;63(23):e202404527. doi: 10.1002/anie.202404527. Epub 2024 Apr 22.
Bimetallic compounds containing direct metal-group 13 element bonds have been shown to display unprecedented patterns of cooperative reactivity towards small molecules, which can be influenced by the identity of the group 13 element. In this context, we present here a systematic appraisal of group 13 metallo-ligands of the type [(NON)E] (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) for E=Al, Ga and In, through a comparison of structural and spectroscopic parameters associated with the trans L or X ligands in linear d complexes of the types LM{E(NON)} and XM'{E(NON)}. These studies are facilitated by convenient syntheses (from the In(I) precursor, InCp) of the potassium indyl species [{K(NON)In}⋅KCp] (1) and [(18-crown-6)KCp] [(NON)In] (1'), and lead to the first structural characterisation of Ag-In and Hg-E (E=Al, In) covalent bonds. The resulting structural, spectroscopic and quantum chemical probes of Ag/Hg complexes are consistent with markedly stronger σ-donor capabilities of the aluminyl ligand, [(NON)Al], over its gallium and indium counterparts.
含有直接金属-第13族元素键的双金属化合物已被证明对小分子表现出前所未有的协同反应模式，这种模式会受到第13族元素身份的影响。在此背景下，我们通过比较与LM{E(NON)}和XM'{E(NON)}类型的线性d配合物中的反式L或X配体相关的结构和光谱参数，对E为Al、Ga和In的[(NON)E]（NON = 4,5-双(2,6-二异丙基苯胺基)-2,7-二叔丁基-9,9-二甲基氧杂蒽）类型的第13族金属配体进行了系统评估。通过方便的合成方法（从In(I)前体InCp）合成了吲哚钾物种[{K(NON)In}⋅KCp] (1)和[(18-冠-6)KCp] [(NON)In] (1')，促进了这些研究，并首次对Ag-In和Hg-E（E = Al、In）共价键进行了结构表征。所得的Ag/Hg配合物的结构、光谱和量子化学探针结果表明，铝基配体[(NON)Al]的σ供体能力明显强于其镓和铟对应物。
