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Metallacycles

Breaking the rules

Nature Chemistry volume 5, pages 649–650 (2013)Cite this article

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Chemists have long been interested in synthesizing compounds that push the boundaries of conventional molecular structure. Incorporating metal centres into the ring unit of highly strained and unsaturated cyclic molecules can help reduce strain — a tactic that has now been used to render a previously inaccessible metallapentalyne isolable.

Owing to the fundamental rules of orbital symmetry, alkynes (RC≡CR), allenes (R2C=C=CR2) and cumulenes (such as R2C=C=C=CR2) are linear, hence incorporation of these unsaturated structural motifs into small carbocyclic ring systems significantly deforms their geometry and causes enormous ring strain. However, synthetic chemists have always been driven by a “desire to make the molecule that violates the norm”1, and so ever more exotic, more unstable hydrocarbon structures have been created.

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Figure 1: Selected examples for exotic four- and five-membered metallacycles:

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Authors and Affiliations

  1. Torsten Beweries and Uwe Rosenthal are at the Leibniz Institute for Catalysis at the University of Rostock (LIKAT), Albert-Einstein-Str. 29a, 18059 Rostock, Germany,

    Torsten Beweries & Uwe Rosenthal

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  1. Torsten Beweries
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  2. Uwe Rosenthal
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Correspondence to Torsten Beweries or Uwe Rosenthal.

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Beweries, T., Rosenthal, U. Breaking the rules. Nature Chem 5, 649–650 (2013). https://doi.org/10.1038/nchem.1702

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