Disilene–Silylene Interconversion: A Synthetically Accessible Acyclic Bis(silyl)silylene

Silylenes have recently shown fascinating reactivity patterns, which are normally observed almost exclusively for transition-metal complexes. In particular, very reactive representatives are considered to be promising candidates, which may become powerful and economical alternatives for catalytic applications in the future. Here, we present the isolation of an equilibrium mixture consisting of a tetrasilyldisilene and its isomeric bis­(silyl)­silylene, the first isolable silylene of this type. Preliminary investigations demonstrate the extreme inherent reactivity via facile small-molecule activation even under very mild conditions. Thus, the oxidative addition of challenging targets such as H2 and NH3 was achieved. In addition, by synthesizing donor-stabilized bis­(silyl)­silylenes we gained further insights into the disilene–silylene rearrangement by 1,2-silyl migrations. Thorough theoretical calculations support the observed experimental results.硅烯（silylene）近期展现出极具研究价值的反应活性特征，这类活性此前几乎仅在过渡金属配合物中被观测到。其中，高活性的硅烯衍生物被视为极具潜力的候选材料，未来有望成为催化应用中高效且经济的替代方案。本文报道了一种平衡混合物的分离工作，该混合物由四硅基二硅烯与其异构体双(硅基)硅烯组成，这是此类中首例可分离的硅烯。初步研究表明，即便在极为温和的条件下，该化合物也能通过简便的小分子活化过程展现出极强的本征反应活性：例如成功实现了H₂与NH₃等具有挑战性底物的氧化加成。此外，通过合成给体稳定化的双(硅基)硅烯，我们对1,2-硅基迁移介导的二硅烯-硅烯重排反应获得了进一步认知。系统的理论计算验证了所观测到的实验结果。