A good catch: N‐Heterocyclic carbenes (NHCs) form stable adducts with nitrous oxide (N2O) under mild reaction conditions. The adducts display unique reactivity as evidenced by an alkylation reaction which leads to a rupture of the NN bond.

The synthesis of topologically complex structures, such as links and knots, is one of the current challenges in supramolecular chemistry. The so-called Solomon link consists of two doubly interlocked rings. Despite being a rather simple link from a topological point of view, only few molecular versions of this link have been described so far. Here, we report the quantitative synthesis of a giant molecular Solomon link from 30 subcomponents. The highly charged structure is formed by assembly of 12 cis-blocked Pt(2+) complexes, six Cu(+) ions, and 12 rigid N-donor ligands. Each of the two interlocked rings is composed of six repeating Pt(ligand) units, while the six Cu(+) ions connect the two rings. With a molecular weight of nearly 12 kDa and a diameter of 44.2 Å, this complex is the largest non-DNA-based Solomon link described so far. Furthermore, it represents a molecular version of a "stick link".

Ein neues interdisziplinäres Forschungsgebiet ist die Biometallorganische Chemie; sie befaßt sich mit der Einführung von metallorganischen Fragmenten in Biomoleküle (siehe z. B. Struktur rechts). Die „klassischen”︁ α‐Aminosäure‐ und Peptidliganden haben sich dabei als besonders vielseitig erwiesen und eröffnen unter anderem einen Zugang zu stereochemisch interessanten Verbindungen. α‐Aminosäuren und Peptide können durch metallorganische Verbindungen synthetisiert, markiert, stabilisiert oder aktiviert werden.

Thorium redox chemistry is extremely scarce due to the high stability of ThIV. Here we report two unique examples of thorium arenide complexes prepared by reduction of a ThIV‐siloxide complex in presence of naphthalene, the mononuclear arenide complex [K(OSi(OtBu)3)3Th(η6‐C10H8)] (1) and the inverse‐sandwich complex [K(OSi(OtBu)3)3Th]2(μ‐η6,η6‐C10H8)] (2). The electrons stored in these complexes allow the reduction of a broad range of substrates (N2O, AdN3, CO2, HBBN). Higher reactivity was found for the complex 1 which reacts with the diazoolefin IDipp=CN2 to yield the unexpected ThIV amidoalkynyl complex 5 via a terminal N‐heterocyclic vinylidene intermediate. This work showed that arenides can act as convenient redox‐active ligands for implementing thorium‐ligand cooperative multielectron transfer and that the reactivity can be tuned by the arenide binding mode.

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