Since the prediction of the existence of metallabenzenes in 1979, metallaaromatic chemistry has developed rapidly, due to its importance in both experimental and theoretical fields. Now six major types of metallaromatic compounds, metallabenzenes, metallabenzynes, heterometallaaromatics, dianion metalloles, metallapentalenes and metallapentalynes (also termed carbolongs), and spiro metalloles, have been reported and extensively studied. Their parent organic analogues may be aromatic, non-aromatic, or even anti-aromatic. These unique systems not only enrich the large family of aromatics, but they also broaden our understanding and extend the concept of aromaticity. This review provides a comprehensive overview of metallaaromatic chemistry. We have focused on not only the six major classes of metallaaromatics, including the main-group-metal-based metallaaromatics, but also other types, such as metallacyclobutadienes and metallacyclopropenes. The structures, synthetic methods, and reactivities are described, their applications are covered, and the challenges and future prospects of the area are discussed. The criteria commonly used to judge the aromaticity of metallaaromatics are presented.

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Where is my iron? The synthesis, structure, and reactivity of small‐molecule models of [Fe]‐hydrogenase are described. These models feature the intriguing acylmethylpyridinyl ligands found exclusively in the enzyme.

A [Fe(II)Fe(II)] dithiolate complex containing acyl and carbonyl ligands was synthesized. The diiron complex reacted with phosphine, cyanide, isocyanide, and CO to give monomeric Fe(II) complexes reproducing the first coordination sphere of the active site of [Fe]-hydrogenase (H(2)-forming methylene-tetrahydromethanopterin dehydrogenase, Hmd) in various states. All the acyl and carbonyl carbons in the diiron complex underwent facile isotopic exchange with (13)CO via monomeric Fe tricarbonyl intermediates.

Wir stellen eine RhIII‐katalysierte C‐H‐Aktivierung/Abfangcyclisierung vor, an der eine nukleophile Addition einer C(sp3)‐Rh‐Spezies an polarisierte Doppelbindungen beteiligt ist. Dies ist die erste intermolekulare katalytische Methode zur direkten Synthese von 1‐Aminoindolinen mit großer Substratbreite und unter milden Reaktionsbedingungen.

What's your number? The synthesis, structure, and reactivity of a five‐coordinate model complex of [Fe]‐hydrogenase are described. The work suggests that the iron center in [Fe]‐hydrogenases could be five‐coordinate in the resting state.

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Rhodium complexes can be homogeneously immobilized on functionalized graphene oxide through coordination interaction. The obtained catalyst can be readily recycled and shows enhanced activity in the catalytic hydrogenation of cyclohexene.