英国牛津大学Aldridge, Simon团队报道了在[Be-Be]²⁺上通过复分解形成的一种亲核的铍基络合物。相关研究成果于2024年5月17日发表在国际知名学术期刊《自然—化学》。

由于其高毒性，人们对第四元素铍的化学性质知之甚少。然而，由于最轻的元素为化学键的基本模型提供了基础，因此需要对铍的性质有更深入的了解。在这种情况下，同元素Be–Be键的化学性质具有根本意义。

该文研究了具有Be–Be键的稳定配合物双铍烯（1；CpBeBeCp）的配体复分解化学。这些研究产生了两种具有Be–Be键的配合物：Cp*BeBeCp (2) and [K{(HCDippN)₂BO}₂]BeBeCp (3; Dipp=2,6-二异丙基苯基）。量子化学计算表明，3中的Be–Be键被极化到这样一种程度，即络合物可以被配制成混合氧化态Be0/BeII络合物。相应地，通过与sp2–sp3二硼烷的反应性类似，证明了3可以将“绿柱石”阴离子[BeCp]转移到有机底物上。

事实上，该项工作揭示了铍和硼的单元素键合键之间惊人的相似性，尽管这些元素具有各自的金属和非金属性质。

附：英文原文

Title: A nucleophilic beryllyl complex via metathesis at [Be–Be]2+

Author: Boronski, Josef T., Crumpton, Agamemnon E., Roper, Aisling F., Aldridge, Simon

Issue&Volume: 2024-05-17

Abstract: 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)2BO}2]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 Be0/BeII complex. Correspondingly, it is demonstrated that 3 can transfer the ‘beryllyl’ anion, [BeCp], to an organic substrate, by analogy with the reactivity of sp2–sp3 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.

DOI: 10.1038/s41557-024-01534-9

Source: https://www.nature.com/articles/s41557-024-01534-9