Boronski Josef T, Crumpton Agamemnon E, Roper Aisling F, Aldridge Simon
Chemistry Research Laboratory Department of Chemistry, University of Oxford, Oxford, UK.
Nat Chem. 2024 Aug;16(8):1295-1300. doi: 10.1038/s41557-024-01534-9. Epub 2024 May 17.
Owing to its high toxicity, the chemistry of element number four, beryllium, is poorly understood. However, as the lightest elements provide the basis for fundamental models of chemical bonding, there is a need for greater insight into the properties of beryllium. In this context, the chemistry of the homo-elemental Be-Be bond is of fundamental interest. Here the ligand metathesis chemistry of diberyllocene (1; CpBeBeCp)-a stable complex with a Be-Be bond-has been investigated. These studies yield two complexes with Be-Be bonds: Cp*BeBeCp (2) and [K{(HCDippN)BO}]BeBeCp (3; Dipp = 2,6-diisopropylphenyl). Quantum chemical calculations indicate that the Be-Be bond in 3 is polarized to such an extent that the complex could be formulated as a mixed-oxidation state Be/Be complex. Correspondingly, it is demonstrated that 3 can transfer the 'beryllyl' anion, [BeCp], to an organic substrate, by analogy with the reactivity of sp-sp diboranes. Indeed, this work reveals striking similarities between the homo-elemental bonding linkages of beryllium and boron, despite the respective metallic and non-metallic natures of these elements.
由于其高毒性,元素周期表中四号元素铍的化学性质鲜为人知。然而,由于最轻的元素为化学键的基本模型提供了基础,因此有必要更深入地了解铍的性质。在此背景下,同元素的Be-Be键的化学性质具有根本重要性。本文研究了二茂铍(1;CpBeBeCp)——一种具有Be-Be键的稳定配合物——的配体复分解化学。这些研究得到了两种具有Be-Be键的配合物:Cp*BeBeCp(2)和[K{(HCDippN)BO}]BeBeCp(3;Dipp = 2,6-二异丙基苯基)。量子化学计算表明,3中的Be-Be键极化程度很高,以至于该配合物可被表述为混合氧化态的Be/Be配合物。相应地,研究表明3能够将“铍基”阴离子[BeCp]转移至有机底物,这与sp-sp二硼烷的反应活性类似。实际上,这项工作揭示了铍和硼的同元素键合之间存在显著相似性,尽管这两种元素分别具有金属和非金属性质。